Examples of the chelating ion exchangers of thiosemicarbazide, piperazine and tetrazine functional groups and their characteristic.
\\n\\n
IntechOpen was founded by scientists, for scientists, in order to make book publishing accessible around the globe. Over the last two decades, this has driven Open Access (OA) book publishing whilst levelling the playing field for global academics. Through our innovative publishing model and the support of the research community, we have now published over 5,700 Open Access books and are visited online by over three million academics every month. These researchers are increasingly working in broad technology-based subjects, driving multidisciplinary academic endeavours into human health, environment, and technology.
\\n\\nBy listening to our community, and in order to serve these rapidly growing areas which lie at the core of IntechOpen's expertise, we are launching a portfolio of Open Science journals:
\\n\\nAll three journals will publish under an Open Access model and embrace Open Science policies to help support the changing needs of academics in these fast-moving research areas. There will be direct links to preprint servers and data repositories, allowing full reproducibility and rapid dissemination of published papers to help accelerate the pace of research. Each journal has renowned Editors in Chief who will work alongside a global Editorial Board, delivering robust single-blind peer review. Supported by our internal editorial teams, this will ensure our authors will receive a quick, user-friendly, and personalised publishing experience.
\\n\\n"By launching our journals portfolio we are introducing new, dedicated homes for interdisciplinary technology-focused researchers to publish their work, whilst embracing Open Science and creating a unique global home for academics to disseminate their work. We are taking a leap toward Open Science continuing and expanding our fundamental commitment to openly sharing scientific research across the world, making it available for the benefit of all." Dr. Sara Uhac, IntechOpen CEO
\\n\\n"Our aim is to promote and create better science for a better world by increasing access to information and the latest scientific developments to all scientists, innovators, entrepreneurs and students and give them the opportunity to learn, observe and contribute to knowledge creation. Open Science promotes a swifter path from research to innovation to produce new products and services." Alex Lazinica, IntechOpen founder
\\n\\nIn conclusion, Natalia Reinic Babic, Head of Journal Publishing and Open Science at IntechOpen adds:
\\n\\n“On behalf of the journal team I’d like to thank all our Editors in Chief, Editorial Boards, internal supporting teams, and our scientific community for their continuous support in making this portfolio a reality - we couldn’t have done it without you! With your support in place, we are confident these journals will become as impactful and successful as our book publishing program and bring us closer to a more open (science) future.”
\\n\\nWe invite you to visit the journals homepage and learn more about the journal’s Editorial Boards, scope and vision as all three journals are now open for submissions.
\\n\\nFeel free to share this news on social media and help us mark this memorable moment!
\\n\\n\\n"}]',published:!0,mainMedia:{caption:"",originalUrl:"/media/original/237"}},components:[{type:"htmlEditorComponent",content:'
After years of being acknowledged as the world's leading publisher of Open Access books, today, we are proud to announce we’ve successfully launched a portfolio of Open Science journals covering rapidly expanding areas of interdisciplinary research.
\n\n\n\nIntechOpen was founded by scientists, for scientists, in order to make book publishing accessible around the globe. Over the last two decades, this has driven Open Access (OA) book publishing whilst levelling the playing field for global academics. Through our innovative publishing model and the support of the research community, we have now published over 5,700 Open Access books and are visited online by over three million academics every month. These researchers are increasingly working in broad technology-based subjects, driving multidisciplinary academic endeavours into human health, environment, and technology.
\n\nBy listening to our community, and in order to serve these rapidly growing areas which lie at the core of IntechOpen's expertise, we are launching a portfolio of Open Science journals:
\n\nAll three journals will publish under an Open Access model and embrace Open Science policies to help support the changing needs of academics in these fast-moving research areas. There will be direct links to preprint servers and data repositories, allowing full reproducibility and rapid dissemination of published papers to help accelerate the pace of research. Each journal has renowned Editors in Chief who will work alongside a global Editorial Board, delivering robust single-blind peer review. Supported by our internal editorial teams, this will ensure our authors will receive a quick, user-friendly, and personalised publishing experience.
\n\n"By launching our journals portfolio we are introducing new, dedicated homes for interdisciplinary technology-focused researchers to publish their work, whilst embracing Open Science and creating a unique global home for academics to disseminate their work. We are taking a leap toward Open Science continuing and expanding our fundamental commitment to openly sharing scientific research across the world, making it available for the benefit of all." Dr. Sara Uhac, IntechOpen CEO
\n\n"Our aim is to promote and create better science for a better world by increasing access to information and the latest scientific developments to all scientists, innovators, entrepreneurs and students and give them the opportunity to learn, observe and contribute to knowledge creation. Open Science promotes a swifter path from research to innovation to produce new products and services." Alex Lazinica, IntechOpen founder
\n\nIn conclusion, Natalia Reinic Babic, Head of Journal Publishing and Open Science at IntechOpen adds:
\n\n“On behalf of the journal team I’d like to thank all our Editors in Chief, Editorial Boards, internal supporting teams, and our scientific community for their continuous support in making this portfolio a reality - we couldn’t have done it without you! With your support in place, we are confident these journals will become as impactful and successful as our book publishing program and bring us closer to a more open (science) future.”
\n\nWe invite you to visit the journals homepage and learn more about the journal’s Editorial Boards, scope and vision as all three journals are now open for submissions.
\n\nFeel free to share this news on social media and help us mark this memorable moment!
\n\n\n'}],latestNews:[{slug:"webinar-introduction-to-open-science-wednesday-18-may-1-pm-cest-20220518",title:"Webinar: Introduction to Open Science | Wednesday 18 May, 1 PM CEST"},{slug:"step-in-the-right-direction-intechopen-launches-a-portfolio-of-open-science-journals-20220414",title:"Step in the Right Direction: IntechOpen Launches a Portfolio of Open Science Journals"},{slug:"let-s-meet-at-london-book-fair-5-7-april-2022-olympia-london-20220321",title:"Let’s meet at London Book Fair, 5-7 April 2022, Olympia London"},{slug:"50-books-published-as-part-of-intechopen-and-knowledge-unlatched-ku-collaboration-20220316",title:"50 Books published as part of IntechOpen and Knowledge Unlatched (KU) Collaboration"},{slug:"intechopen-joins-the-united-nations-sustainable-development-goals-publishers-compact-20221702",title:"IntechOpen joins the United Nations Sustainable Development Goals Publishers Compact"},{slug:"intechopen-signs-exclusive-representation-agreement-with-lsr-libros-servicios-y-representaciones-s-a-de-c-v-20211123",title:"IntechOpen Signs Exclusive Representation Agreement with LSR Libros Servicios y Representaciones S.A. de C.V"},{slug:"intechopen-expands-partnership-with-research4life-20211110",title:"IntechOpen Expands Partnership with Research4Life"},{slug:"introducing-intechopen-book-series-a-new-publishing-format-for-oa-books-20210915",title:"Introducing IntechOpen Book Series - A New Publishing Format for OA Books"}]},book:{item:{type:"book",id:"7795",leadTitle:null,fullTitle:"Artificial Intelligence - Scope and Limitations",title:"Artificial Intelligence",subtitle:"Scope and Limitations",reviewType:"peer-reviewed",abstract:"Artificial intelligence (AI) is a potent buzzword and happening technology which has greatly impacted the lifestyle of every human being either directly or indirectly and is shaping the future of tomorrow. In fact, AI is fast becoming an intrinsic part of our daily life and is not confined to university research labs, even if remarkable progress has been made in this domain. The benefit of this phenomenon is widely recognized in diversified areas, ranging from medicine to security to consumer applications and business, and resulting in improvements in the quality of life of humankind. Every new disruptive technology has its own pros and cons and AI is no exception to this rule. Privacy, data protection, and the rights of individuals pose social and ethical challenges.",isbn:"978-1-78985-936-2",printIsbn:"978-1-78985-935-5",pdfIsbn:"978-1-83962-124-6",doi:"10.5772/intechopen.77611",price:100,priceEur:109,priceUsd:129,slug:"artificial-intelligence-scope-and-limitations",numberOfPages:78,isOpenForSubmission:!1,isInWos:1,isInBkci:!1,hash:"7e536b4fe8982ca9015228fe6f58c6ea",bookSignature:"Dinesh G. Harkut",publishedDate:"April 24th 2019",coverURL:"https://cdn.intechopen.com/books/images_new/7795.jpg",numberOfDownloads:5605,numberOfWosCitations:4,numberOfCrossrefCitations:4,numberOfCrossrefCitationsByBook:1,numberOfDimensionsCitations:9,numberOfDimensionsCitationsByBook:1,hasAltmetrics:1,numberOfTotalCitations:17,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"June 13th 2018",dateEndSecondStepPublish:"July 4th 2018",dateEndThirdStepPublish:"September 2nd 2018",dateEndFourthStepPublish:"November 21st 2018",dateEndFifthStepPublish:"January 20th 2019",currentStepOfPublishingProcess:5,indexedIn:"1,2,3,4,5,6,7",editedByType:"Edited by",kuFlag:!1,featuredMarkup:null,editors:[{id:"216122",title:"Dr.",name:"Dinesh G.",middleName:null,surname:"Harkut",slug:"dinesh-g.-harkut",fullName:"Dinesh G. Harkut",profilePictureURL:"https://mts.intechopen.com/storage/users/216122/images/system/216122.png",biography:"Dr. Dinesh G. Harkut is Associate Professor at Prof Ram Meghe College of Engineering & Management (PRMCEAM), Badnera, India, in the Computer Science and Engineering Department. He obtained a bachelor’s degree, a master’s of engineering (CSE), and a PhD (CSE) from SGBAU Amravati University, Maharashtra, India. He also holds a master’s degree and PhD in Business Administration.\nHis primary research interests are in artificial intelligence, big data, analytics, embedded systems, and e-commerce. He has supervised eighteen master’s degree and twenty-four bachelor’s degree students. He has published forty-seven papers in refereed journals and published six books with international publishers. He has also organized various workshops, sessions, conferences, and trainings. He has two patents filed and published in his name in India. \nHe is a member of the Board of Studies (Computer Science and Engineering) and a recognized PhD supervisor at SGBAU Amravati University, Maharashtra, India. He holds membership in various professional bodies including the Institution of Electronics and Telecommunication Engineers (IETE), New Delhi; International Society for Technology in Education (ISTE), New Delhi; Universal Association of Computer and Electronics Engineers (UACEE), USA; International Economics Development and Research Center (IEDRC), Hong Kong; International Association of Engineers (IAENG), Hong Kong; and the European Alliance for Innovation, Belgium.",institutionString:"Prof Ram Mehge College of Engineering and Management",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"3",totalChapterViews:"0",totalEditedBooks:"4",institution:{name:"Sant Gadge Baba Amravati University",institutionURL:null,country:{name:"India"}}}],equalEditorOne:null,equalEditorTwo:null,equalEditorThree:null,coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"87",title:"Artificial Intelligence",slug:"computer-and-information-science-artificial-intelligence"}],chapters:[{id:"66147",title:"Introductory Chapter: Artificial Intelligence - Challenges and Applications",doi:"10.5772/intechopen.84624",slug:"introductory-chapter-artificial-intelligence-challenges-and-applications",totalDownloads:1586,totalCrossrefCites:3,totalDimensionsCites:5,hasAltmetrics:1,abstract:null,signatures:"Dinesh G. Harkut and Kashmira Kasat",downloadPdfUrl:"/chapter/pdf-download/66147",previewPdfUrl:"/chapter/pdf-preview/66147",authors:[null],corrections:null},{id:"64306",title:"Intention to Use WhatsApp",doi:"10.5772/intechopen.81999",slug:"intention-to-use-whatsapp",totalDownloads:1059,totalCrossrefCites:1,totalDimensionsCites:4,hasAltmetrics:1,abstract:"More than 1.8 billion people use WhatsApp nowadays, out of which 70% uses it daily. In this scenario, this study seeks modeling the variables that positively influence the intention to use WhatsApp. To this end, 579 surveys based on the unified theory of acceptance and use of technology are conducted. The descriptive results show that individuals use WhatsApp mainly motivated by leisure. In this sense, according to the structural equation model, the variable with the greatest influence on behavioral intention is hedonic motivation, followed by social influence, performance expectancy, and effort expectancy. These results indicate that most people use WhatsApp principally because they find it fun, enjoyable, and very entertaining, something more inherent to an entertainment application than to a messaging application. Nevertheless, a cluster analysis indicates the existence of two consumer segments: one showing a certain indifference and disagreement regarding the usefulness of WhatsApp for their activities and duties and the other manifesting that it uses WhatsApp not only for leisure but also for work, academic, and informative reasons. These differences in consumer drivers might have a great impact on WhatsApp and its competition marketing strategies.",signatures:"Cristobal Fernández-Robin, Diego Yáñez and Scott McCoy",downloadPdfUrl:"/chapter/pdf-download/64306",previewPdfUrl:"/chapter/pdf-preview/64306",authors:[null],corrections:null},{id:"65222",title:"Information and Communication Systems Including Artificial Intelligence and Big Data as Objects of International Legal Protection",doi:"10.5772/intechopen.83565",slug:"information-and-communication-systems-including-artificial-intelligence-and-big-data-as-objects-of-i",totalDownloads:975,totalCrossrefCites:0,totalDimensionsCites:0,hasAltmetrics:0,abstract:"The objective of this study is identifying prospective for international legal protection of information and communication systems including artificial intelligence on the universal and regional levels, and analysis of legal instruments for protection of artificial intelligence and Big Data in the context of regulation of relations in the global information society. A complex of general scientific and philosophical methods, including the logical, comparative-legal, formal-legal, systemic-structural, and problematic-theoretical methods, as well as methods of analysis and synthesis, generalization and description were used in the research. It was found that the existing international agreements in the field of intellectual property protection take no account of the particular features of protection of complex objects. Complex objects comprise information and communication systems including artificial intelligence and Big Data. There is an objective necessity to establish a legal regime for complex objects on the universal level. The findings can be used in activities of international organizations in execution of their functions of unification and harmonization of the international information law.",signatures:"Valentina Petrovna Talimonchik",downloadPdfUrl:"/chapter/pdf-download/65222",previewPdfUrl:"/chapter/pdf-preview/65222",authors:[{id:"248931",title:"Dr.",name:"Valentina",surname:"Talimonchik",slug:"valentina-talimonchik",fullName:"Valentina Talimonchik"}],corrections:null},{id:"64350",title:"Prediction of Cancer Patient Outcomes Based on Artificial Intelligence",doi:"10.5772/intechopen.81872",slug:"prediction-of-cancer-patient-outcomes-based-on-artificial-intelligence",totalDownloads:1180,totalCrossrefCites:0,totalDimensionsCites:0,hasAltmetrics:0,abstract:"Knowledge-based outcome predictions are common before radiotherapy. Because there are various treatment techniques, numerous factors must be considered in predicting cancer patient outcomes. As expectations surrounding personalized radiotherapy using complex data have increased, studies on outcome predictions using artificial intelligence have also increased. Representative artificial intelligence techniques used to predict the outcomes of cancer patients in the field of radiation oncology include collecting and processing big data, text mining of clinical literature, and machine learning for implementing prediction models. Here, methods of data preparation and model construction to predict rates of survival and toxicity using artificial intelligence are described.",signatures:"Suk Lee, Eunbin Ju, Suk Woo Choi, Hyungju Lee, Jang Bo Shim,\nKyung Hwan Chang, Kwang Hyeon Kim and Chul Yong Kim",downloadPdfUrl:"/chapter/pdf-download/64350",previewPdfUrl:"/chapter/pdf-preview/64350",authors:[null],corrections:null},{id:"64304",title:"Team Exploration of Environments Using Stochastic Local Search",doi:"10.5772/intechopen.81902",slug:"team-exploration-of-environments-using-stochastic-local-search",totalDownloads:805,totalCrossrefCites:0,totalDimensionsCites:0,hasAltmetrics:0,abstract:"We investigate the use of Stochastic Local Search (SLS) technique to explore environments where agents? knowledge and the time to explore such environments are limited. We extend a work that uses evolutionary algorithms to evolve teams in simulated environments. Our work proposes a formalization of the concept of state and neighborhood for SLS and provides evaluation of agents? teams using number of interesting cells. Further, we modify the environments to include goals that are randomly distributed among interesting cells. Agents in this case are then required to search for goals. Experiments using teams of different sizes show the effectiveness of our technique. Teams were able to complete exploration of more than 70% of the environments, while in the best cases, they were able to complete explorations of more than 80% of the environments within limited time steps. These results compare with those of the previous work. It is interesting to note that all teams of agents were able to find on average all the goals in the three environments when the size of the grid is 12. This is a 100% achievement by the agents? teams. However, performance can be seen to degrade as the environments? sizes become larger.",signatures:"Ramoni O. Lasisi and Robert DuPont",downloadPdfUrl:"/chapter/pdf-download/64304",previewPdfUrl:"/chapter/pdf-preview/64304",authors:[null],corrections:null}],productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},subseries:null,tags:null},relatedBooks:[{type:"book",id:"9966",title:"Dynamic Data Assimilation",subtitle:"Beating the Uncertainties",isOpenForSubmission:!1,hash:"e7fde2a36354a2f5a4282fdf9c743380",slug:"dynamic-data-assimilation-beating-the-uncertainties",bookSignature:"Dinesh G. Harkut",coverURL:"https://cdn.intechopen.com/books/images_new/9966.jpg",editedByType:"Edited by",editors:[{id:"216122",title:"Dr.",name:"Dinesh G.",surname:"Harkut",slug:"dinesh-g.-harkut",fullName:"Dinesh G. 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\r\n\r\n\tGlaucoma is one of the leading causes of irreversible vision loss and a huge socioeconomic burden to the society. Early detection and prompt intervention with intraocular pressure lowering medications is the main stay. This is accomplished by both medical and/or surgical techniques and both these methodologies have seen great advances. This book will cover both. There are new combination agents and sustained released drugs that are FDA approved. Additionally, there are new drugs in development and potentially neuroprotective agents or adjunctive therapies that are in the horizon.
\r\n\r\n\tSurgical procedures has seen the greatest developments in the last decade with numerous new stents and micro invasive procedures that have been FDA approved. These have led to decrease in number of medications that are needed to achieve the target pressure to prevent progressive damage in glaucoma.
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There is still another basis of ion exchangers division conditioned by historical development of this area, i.e. according to their origin – natural, semi-synthetic and synthetic [1–5].
Small amounts of noble elements in nature and constant impoverishment of their natural resources result in significant importance of physicochemical methods used for platinum metal ions recovery from secondary resources e.g. worn car exhaust gas convertor, chemical catalysts, stomatology alloys as well as waste waters and waters of refinery origin. Noble metals recovery from such raw materials requires individual approach and application of selective methods of their removal. Moreover, worse quality of these raw materials makes removal of pure noble metals more difficult. Determination of noble metals, particularly platinum ones in the above-mentioned materials, geological samples and synthetic mixtures together with other elements is of significant importance nowadays. Liquid–solid phase extraction (SPE) has some advantages compared to liquid–liquid extraction. Among others, it is faster, cheaper, uses small amounts of reagents and above all its automatization is easier. Moreover, its simple performance and high enrichment coefficients decide about its common laboratory application. SPE uses solid sorbents which should be characterized by not only high capacity towards metal ions under determination but also large selectivity and suitable sorption and desorption kinetics.
Synthetic ion exchange resins are widely applied in platinum metal ions enrichments. Among them of particular interest are cation exchangers, chelating ion exchangers and anion exchangers of different basicity of functional groups. Ion exchange selectivity depends on the kind and number of functional groups of ion exchanger as well as cross-linking and composition of external electrolyte solution composition from which concentration proceeds. Of these types of ion exchangers, the most effective are monofunctional ones, which ensure the same strength of bonding ions with the ion exchanger surface due to the presence of one type of groups which does not make equilibrium establishment difficult. Complexity of platinum carrying samples for enrichment makes it necessary to separate a component under determination due to large interference of components present in the analyte. In the chloride systems, ion exchange enables platinum metal ions separation not only from their mixtures but also from other metals. In the hydrogen chloride acid solutions, most platinum metal ions are present in the form of anion chloride complexes; therefore they are retained by strongly basic anion exchangers. Anion exchangers enable selective removal of platinum metal ions from solutions of other metals; however, there appear some problems with their elution due to strong sorption of platinum metal ions. It can often occur that recovery is not quantitative or rendered difficult. Such situation arises because of stable ion pairs formation between anionic complexes and the quaternary ammonium groups of the anion exchanger. Reduction of noble metal ions can proceed in the ion exchanger phase which also affects incomplete recovery. Some difficulties with determination can result from different behaviour of new and ‘old’ solutions which is connected with the hydrolysis process in the solution. This reflects mainly to rhodium or iridium chloride complexes because they have the greatest tendency towards hydrolysis. Using cation exchangers, rare earth elements, transient metals as well as alkali metals and alkaline earth family form weakly anionic or stable cationic complexes therefore they are retained on the cation exchange deposit whereas platinum metals go through the column not being retained by the cation exchangers making separation of the above-mentioned metal ions possible.
There are numerous reports in the literature about cation exchangers application in concentration and separation of trace amounts of platinum metal ions. Ion exchange is widely applied also for control of bound and free platinum contents in the serum added in the cis-platinum form. After ultrafiltration, ethylenediamine was added to form complexes which are sorbed on cation exchange disks. Platinum ions were desorbed from the disks by means of 5 M HCl and determined using the AAS method. The detection limit was 35 μg/dm3 [6].
Besides the above-described procedures, there are separation methods using cation exchangers. As commonly known platinum metals tend to form anion complexes in the chloride systems, therefore partition coefficient values should not be high [7–9]. Much higher values of partition coefficients of platinum metal ions can be obtained by the addition of thiourea which results in cation complexes formation [9].
The polystyrenesulfone cation exchanger Dowex 50Wx8 in the hydrogen form was used for the determination of metals from the platinum group in ores and concentrates. Before ion exchange stage, noble metals in metallic copper were collected. The obtained alloy was digested in
Separation of noble metals can be conducted on the cation exchangers from the thiourea systems. Separation of microquantities of various pairs of noble metal ions was made using the polystyrene sulfone cation exchanger Bio-Rad AG 50Wx4 in the hydrogen form. Pd(II) and Au(I), Pd(II) and Pt(II) ions as well as the Rh(III), Au(I), Pt(II) and Ag(I) mixture were separated using the acetate-thiourea solutions in the hydrochloric or hydrobromic acid medium [39]. Platinum(II) and palladium(II) ions were separated from aluminium ions using also the cation exchanger Bio Rad AG50Wx4 in the hydrogen form. Aluminium ions as well as Fe, Zn, Pb, U, Ni, Co and Sr ones do not form cationic complexes under experimental conditions, therefore only noble metals are sorbed from 0.1 M thiourea solution in 1.5 M hydrochloric acid solution. 2% Br2 and 1.5 M HCl solution was used for elution of Pt(II) and Pd(II) ions. 0.87 M HBr–0.01 M thiourea solution in 90% acetone proved to be the best eluant towards Pt(II) ions. The presence of Cu(II) and Hg(II) ions is not recommended because of possible co-adsorption with noble metals [40]. It is relatively difficult to separate rhodium(III) ions from platinum(IV) ones in the chloride medium, therefore in some cases it is necessary to change the medium into the nitrate one. Before the separation of platinum(IV) and rhodium(III) ions on the polystyrene-sulfone cation exchanger Varion KS in the hydrogen form, the chloride complexes were in contact with sodium hydroxide at pH 13 for four hours. Then the obtained solution was acidified with 4 M HNO3 to pH 2. Under such conditions, rhodium(III) ions occur in the cation form and platinum(IV) ions in the anion form. Platinum(IV) ions are not retained by the cation exchanger. Rhodium(III) ions can be eluted with 1 M hydrochloric acid from the cation exchanger [41].
Chelating ion exchangers also called complexing ion exchangers are formed by building organic reagents containing organic groups into the ion exchange resin skeleton. Owing to that they possess active chemical groups capable of selective/specific interactions with metal ions in the solution forming chelating complexes when a metal ion can bind with two or a larger number of donor atoms of their functional groups. These ion exchangers are characterized by high selectivity and their sorption capacities depend, among others, on the kind of functional groups, their reciprocal position and spatial configuration (steric effects) and also on physicochemical properties of the polymer matrix [42, 43].
On the huge number of chelating ion exchangers, on a large laboratory and industrial scale, there are produced ion exchangers of functional dithizone, thiourea, isothiourea, aminophosphonic, phosphonic, thiol, amidooxime, aminoacetate, dithiocarbamate, iminodiacetate, thiosemicarbamate groups as well as chelating ion exchangers containing triisobutylphosphine sulfides [44-64].
Chelating ion exchangers of functional dithizone (diphenyl carbamate) groups are widely applied in concentration, separation and recovery of noble metal ions [44–54].
Grote and Kettrup [45–48], by conversion of the ion exchanger of functional dehydrodithizone groups, prepared a chelating resin containing dithizone groups. It was used on both sorption and separation of 27 noble and non-noble ions from acids (HCl, HNO3).They showed very high values of partition coefficients of noble metal ions of the order 104–106 (Pd(II)–7.7×105; Pt(IV)–3.4×105; Au(III)–2.1×105 (0.01 M HCl)) in the whole range of hydrochloric acid (0.01–6 M) as well as Ag(I) (1.1×103) and Hg(II) (5.8×104) ions in diluted nitric(V) acid solutions compared to the values of partition coefficients for non-noble metal ions. Also high values of ion exchange capacities of platinum metals and gold (Au(III) 0.74; Pd(II) 0.68; Pt(II) 0.39; Pt(IV) 0.31; Os(IV) 0.12; Ir(IV) 0.14; Ir(III) 0.02; Ru(III) 0.14; Rh(III) 0.16 mmol/g of the dithizone resin) indicate large selectivity of the resin with dithizone functional groups towards noble metal ions as well as possibility of their application in separation from other non-noble metals. Satisfactory results were obtained using the chelating ion exchanger with dithizone functional group in concentration and recovery of Au(III), Pt(IV) and Pd(II) ions originating from the extraction of sulfide ores, stones and enriched ores. Elution of the above-mentioned ions was conducted by means of 2 M chloric(VII) acid and 5% thiourea solution [44]. There was also made a thorough analysis of desorption of single noble metal ions and their mixtures from the resin with the dithizone functional groups using the following eluents: HCl, HClO4, NH4NO3, NaSCN, (NH2)2CS. Palladium(II) and platinum(IV) ions retained on this resin can be qualitatively desorbed using the thiourea solution [46].
Similar investigations using polyvinylpyridine resin of functional dithizone groups in Pd(II) and Pt(IV) ions concentration in the presence of Au(III), Ni(II) i Hg(II) ions were carried out by Shah and Devi [49]. The values of maximal ion exchange capacities towards palladium and platinum ions were 100 and 250 mg/g of resin, respectively. Separation of the above-mentioned ions from nickel, gold and mercury ions (Pd(II)-Ni(II); Pt(IV)-Au(III); Pt(IV)-Ni(II); Pd(II)-Pt(IV)-Ni(II); Pt(IV)- Au(III)-Hg(II)) was conducted using various eluants 0.1 M HCl + 1% (NH2)2CS (elution of Pd(II)), 0.1 M HCl + 5 % (NH2)2CS (elution of Pt(IV)), 0.2 M CH3COOH (elution of Ni(II)), 5 M HCl + 1 M HNO3 (elution of Au(III)) and 0.5 M HNO3 + 2 % NH4NO3 (elution of Hg(II)).
Modification of the commercially available polyacrylate matrix Diaion HP-2MG with dithizone resulted in the preparation of the selective sorbent towards Pd(II) and Pt(IV) ions. Chwastowska et al. [51] used the above-mentioned sorbent for removal of Pd(II) and Pt(IV) ions from the environmental samples, among others, from road dusts, soil and grass collected from fast traffic routes. After proper preparation, among others, drying (673 K, 1 h) and digestion in
Chelating resin formed by immobilization of sulfonated dithizone on the anion exchanger Amberlite IRA-400 was applied in concentration of heavy metal ions, i.e. Pd(II), Ni(II), Co(II), Cu(II) and Pb(II) in the water samples collected in Japan. The first four elements were determined by the GFAAS technique but Pb(II) by HGAAS. The affinity series of the studied ions towards the present resin is as follows: Pd(II) > Cu(II) > Co(II) > Pb(II) > Ni(II) [52].
Of significant importance are the results of studies on the application of commercial ion exchangers Tulsion of the functional isothiourea and phosphonic groups for removal of Pd(II) ions from nitric(V) acid solutions (0.1–4 M). High values of partition coefficients (particularly in diluted HNO3 (0.1 M) solutions) decreased with the increasing concentration of nitric(V) acid for the ion exchangers Tulsion CH-95, Tulsion CH-96 and Tulsion CH-97. The values of partition coefficients (particularly in diluted HNO3 (0.1 M) solutions) which were >10 000 cm3/g, 1650 cm3/g, 5210 cm3/g for Tulsion CH-95, Tulsion CH-96 and Tulsion CH-97, respectively, decreased with the increasing nitric acid(V) concentration. The selectivity series of the Tulsion ion exchangers towards Pd(II) ions is as follows:
The ion exchangers of the functional thiourea and isothiourea groups, commercially known as Srafion NMRR, Lewatit TP-214 and Purolite S-920, are widely used for the concentration of platinum metal ions [53-61]. Srafion NMRR (Ionac SR-3) exhibits great affinity for Au(III) and Ag(I) as well as Pd(II), Pt(IV), Rh(III), Ru(III), Ir(III) and Os(VI) ions [53-61]. It is applied in the separation of noble metal ions [57], similar to the ion exchangers Monivex which develop high sorption capacity values particularly in the largely acidic solutions (2–6 M HCl) [67]. Lewatit TP-214 was used for the removal Pd(II) ions from two component Pd(II)–Zn(II); Pd(II)–Cu(II)) and multicomponent (Pd(II)–Cu(II)–Zn(II)) chloride solutions [61] and for the removal of Pd(II) ions from chloride solutions (0.1–8.0 – 0,001 M Pd(II)) and chloride–nitrate ones (0.1÷0.9 M HCl – 0.9÷0.1 M HNO3– 0,0011 M Pd(II)) ) [55]. The total ion exchange capacity of Lewatit TP-214 towards Pd(II) ions was from 0.97 mmol/g–3 M HCl to 1.16 mmol/g–0.1 M HCl [55].
Zuo and Muhammed prepared a large number of ion exchangers of the functional thiourea groups by modification of macroporous polystyrene matrices of Bonopore, Amberlite XAD-2, Amberlite XAD-4 as well as the weakly basic anion exchanger Amberlite IR-45 [62]. Newly prepared ion exchangers were used in sorption of Au(III), Ag(I), Cu(II) and Fe(III) ions from one-component chlorides solutions (2 M HCl) and their mixtures (Au(III), Ag(I), Fe(III), Cu(II)), as well as in sorption of platinum metal ions e.g. Pd(II), Pt(IV), Rh(III), etc. The studied ion exchangers are characterized by high selectivity towards noble metal ion, particularly gold and silver in the presence of Cu(II) and Fe(III).
Separation of Pd(II), Cu(II) and Zn(II) ions using the melamine-formaldehyde-thiourea (MFT) resin was presented in [63]. There was proved high selectivity of this resin towards Pd(II) ions, and the obtained values of sorption capacity were 15.29 mg Pd(II)/g (static method) and 1580 μg Pd(II)/g resin (dynamic method). Desorption of ions with studied resin was conducted using 0.5 M thiourea, 0.5 M HCl solutions and the acidified thiourea (0.5 M (NH2)2CS–0.5 M HCl).
The chelating ion exchangers of functional thiol and methylene thiol groups with the commercial names: Chelite S, Duolite GT-73, Imac GT-73, Duolite GT-74, Purolite S-924, Spheron Thiol 1000 and Tulsion CH-97 are widely applied in sorption and separation of noble metal ions [55, 56, 64-69]. Introducing 8-hydroxchinoline (HOxn) and sodium salicylate groups to the methacrylate polymer matrix generates two new chelating ion exchangers Spheron Oxine 1000 and Spheron Salicyl 1000, respectively, which similar to Spheron Thiol 1000 are applied in the separation of Pd(II) and Cu(II) ions. From the determined ion exchange capacities, the affinity series of Spheron ion exchangers towards Pd(II) ions is as follows:
Many authors prove high reactivity of imidazole groups and their derivatives towards metal ions, particularly noble metals ions. For example, VBC-DVB (VBC – vinylbenzene chloride, DVB – divinylbenzene) – recovery of Pd(II) and Pt(IV) ions from chloride solutions (1–2 M HCl) and their separation from Cu(II), Zn(II) and Ni(II); sorption capacity, 1.6–1.7; 1.4–1.5 and 1 mmol of metal/g for the 0.1 M HCl, 1 M HCl and 2 M HCl solutions, respectively; desorption of Pd(II) and Pt(IV) ions, 0.1–0.3 M thiourea solution (desorption effectiveness >98% for Pd(II); 85% for Pt(IV)) [71, 72]; epoxide resin of the functional imidazole groups concentration of trace (20 ng/dm3) amounts of Au(III), Pd(IV) and Ru(III) ions. Noble metal ions can be enriched in a quantitative way (recovery 94.5–100%, pH = 4), desorption: acidified thiourea solutions (16 cm3 6 M HCl, 0.2 g thiourea), recovery 96–99.5% [73], polystyrene-divinylbenzene resin of functional benzimidazole group – separation of heavy metal ions that is Pd(II), Ag(I) and Hg(II) from medical alloys, geological materials, different kinds of waste waters and sludges; sorption capacity: 1 mmol/g for Ag(I) (pH = 4–6), 0.62 mmol/g for Pd(II) (pH = 5–6) and 0.83 mmol/g for Hg(II) (pH = 4–6); desorption: 5% thiourea solution in 0.1 M HClO4 (recovery: Ag(I) and Hg (II) – 100%, Pd(II) – 60%) and 12 M hydrochloric acid solution (recovery: Ag(I) – 45 %, Pd(II) – 100 %, Hg(II) – 65 %) [74]; polystyrene-divinylbenzene resin of Im-NO3 (Im-imidazole) groups – removal of Pd(II) (0.00062 M) form nitric(V) acid solutions (1–5 M HNO3); sorption capacity depends, among others, on the molar ration of initial reagents of chloromethylated resin (I) and 1-methylimidazole (II) at the reagents ratio I:II = 1:1.5 this capacity is the highest (4.06 mmol/g), the total capacity determined form the Langmuir 88 mg/g (3 M HNO3) [75]; resin of functional aminoethylene imidazole (IEA) – concentration of trace amounts of Au(III), Pt(IV), Ir(IV), Pd(II) ions and their separation from Cu(II), Fe(III), Zn(II), Ni(II), Mn(II), Cr(III), Ca(II) and Mg(II) ions; sorption capacity in 2 M HCl solution: 4.0 mmol/g – Au(III), 1.57 mmol/g – Pt(IV), 2.26 mmol/g – Pd(II) and 1.85 mmol/g – Ir(IV) [76].
Table 1 presents the characteristic of chosen chelating ion exchangers of thiosemicarbazide, piperazine and tetrazine functional groups widely applied in the concentration and removal of platinum group ions [77–80].
\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t
Resin of thiosemicarbazide functional groups | \n\t\t\tSeparation of Pd(II), Rh(III), Pt(IV), Ru(III), Ir(III), Au(III), Os(VI), as well as Cu(II), Bi(III), Hg(II), Fe(III) and Al(III) | \n\t\t\tSorption capacities (mmol/g): Pd(II) – 0.78 (pH = 0); Pt(IV) – 0.71 (pH = 0); Ru(III) – 0.685 (1.5 M HCl); Rh(III) – 0.615 (2 M HCl); Ag(I) – 0 (pH = 0) and increase with increasing solution pH, Ir(III) – 0 (pH = 0); Au(III) and Os(VI) are reduced during the contact with the resin; Cu(II), Bi(III), Hg(II), Fe(III) and Al(III) are not retained by the resin; Desorption: 4 M and 9 M HCl as well as 5 % N,N-diphenylthiourea in ethanol | \n\t\t\t[77] | \n\t\t
Resin of amine and 1,2,4,5-tetraazine functional groups | \n\t\t\tPreconcentration and separation of noble metal ions in the amount of 0.001 M in the presence of Zn(II), Co(II), Cu(II), Fe(III), Ni(II) and Cd(II) from acidic solutions of the proportion of noble metal to base metal: 1:1, 1:10, 1:100 | \n\t\t\tSelectivity series: Pd(II) > Au(III) >> Ir(IV) > Os(IV) > Pt(IV) > Ru(III) > Rh(III); Desorption: acidified 5% (NH2)2CS | \n\t\t\t[79] | \n\t\t
Resin of 1-(2-aminethylene)- piperazine functional groups | \n\t\t\tPre-concentration and recovery of Au(III), Pd(II), Ru(III), Os(VI), Pt(IV) and Ir(IV) in the presence of Zn(II), Fe(III), Cu(II) and Ni(II) from chloride solutions | \n\t\t\tSorption capacities for Au(III), Pd(II), Ru(III), Os(VI), Pt(IV) and Ir(IV) equalled to 5.38, 3.67, 3.46, 3.10, 2.46 and 2.24 mmol/g, respectively | \n\t\t\t[80] | \n\t\t
Examples of the chelating ion exchangers of thiosemicarbazide, piperazine and tetrazine functional groups and their characteristic.
Resins of pyridine [81] and α-aminopyridine groups on the polyphenylethylene support [82] were successfully used for the separation of technetium and platinum metals from diluted chloride solutions and in concentration of Pt(IV), Pd(II) and Ir(III) (
Resins of functional amine and guanidine functional groups were successfully used in sorption of Pd(II), Pt(IV) and Au(III) ions from chlorides solutions (initial concentration of each metal was 24 mM). The highest selectivity towards the above-mentioned ions and the possibility of practical application of their recovery are exhibited by the ion exchangers A2 (Au – 99.7; Pt – 108; Pd – 54.3 mg/g), B2 (Au – 94.1; Pt – 104.8; Pd – 48.7 mg/g) and AG2 (Au – 85,1; Pt – 64; Pd – 49.2 mg/g) and BG2 (Au – 74.3; Pt – 76.2; Pd – 48.5 mg/g). The sorption mechanism of Pd(II), Pt(IV) and Au(III) chloro complexes is the combination of coordination interactions of electron nitrogen pair and electrostatic interactions of these ions with the protonated group –NH2 [83].
In the case of the ion exchangers of the same functional groups: amine (D1, D2, D3, D4) and guanidine (D1G, D2G, D3G, D4G) but on the basis of copolymer VBC/AN/DVB (copolymer D), the studies of Pd(II), Pt(IV), Au(III), Cu(II), Ni(II) and Fe(III) ion removal from single and multi-component chloride solutions (0.1–3.0 M HCl) showed that the highest selectivity towards metal ions is exhibited by the resin D4 (sorption capacity 190 mg Au(III)/g, 245 mg Pt(IV)/g and 280 mg Pd(II)/g of the resin), and the selectivity series towards Pd(II) ions is as follows: D4 (117 mg/g) >> D1 > D4G > D1G > D2 = D3G > D2G > D3 (25 mg/g). Recovery of noble metals from multi-component solutions with ten greater excess of Cu(II), Ni(II) and Fe(III) ions was > 95 % [84].
Modification of the macroporous copolymer ACR/ST/DVB (where ACR – acrolein, ST – styrene, DVB – divinylobenzene) using isonicotinic acid hydrazide and hydrazine hydrate results in preparation of new chelating ion exchangers: P-NHZ and P-THZN, respectively [85–87]. These resins exhibited high selectivity towards noble metal ions which allows their separation from common metal ions. The maximal values of sorption capacities obtained in 0.1 M HCl are 3.77 mmol Au(III)/g, 1 mmol Pt(IV)/g, 0.79 mmol Pd(II)/g, 0.72 mmol Ir(III)/g, 0.51 mmol Ru(III)/g, 0.39 mmol Rh(III)/g for the resin P-NHZ and 4.2 mmol Au(III)/g, 1.36 mmol Pd(II)/g, 0.5 mmol Pt(IV)/g, 0.4 mmol Ir(III)/g, 0.31 mmol Rh(III)/g, 0.29 mmol Ru(III)/g for the resin P-THZN, whereas the sorption capacities for common metal ions (Cu(II), Fe(III), Co(II), Ni(II), Cr(III), Zn(II), Mn(II) and Al(III)) are small, in the range 0–0.13 mmol/g for the resin P-NHZ and 0.03–0.32 mmol/g for the resin P-THZD. Desorption of the above-mentioned ions from the P-NHZ and P-THZN was achieved using a 5% thiourea solution in 0.1 M HCl. Quantitative desorption was possible only in the case of Au(III) and Pd(II) from the resin P-NHZ. Another advantage of the ion exchanger P-NHZ over P-THZN is fast kinetics of sorption and easy elution of adsorbed ions [87].
Ge et al. [86] proved high selectivity of the P-NHZ resin towards noble metal ions and possibility of its exploitation for separation and concentration of trace amounts of Pd(II) and Pt(IV) contained in road dust samples. Sorption of the above-mentioned ions on the P-NHZ resin can be conducted also from the HNO3, HF and H3BO3 solutions of the concentration 0.08-1.2 M.
Chelating ion exchangers of functional formazane groups [88–91] based on the styrene divinylbenzene skeleton [58], amino- and chloromethylated polystyrene [91], cellulose [58, 91], saccharose [65] and methacrylate [58] were applied for sorption and separation of platinum metals, gold, mercury, silver and copper. The sorption capacity towards Pd(II), Ag(I) and Hg(II) ions was in the range 0.05–0.06 mmol/g, 0.4–0.9 mmol/g and 0.6–0.8 mmol/g, respectively, for formazane ion exchanger based on cellulose, aminomethylated polystyrene; however, their sorption capacity towards Cu(II) ions was close to zero.
For separation and recovery of Pd(II), Pt(IV) and Au(III), Jermakowicz-Bartkowiak [92] used the resin A7C prepared by the reaction of cyclane (1,4,8,11-tetraazacyclotetradecane) with the copolymer of vinylbenzyl and divinylbenzene chloride (VBC/DVB) obtaining the following sorption capacities: 47.4 (S0), 47.4 (S1) mg Au(III)/g, 48.1 (S0), 47.5 (S1) mg Pt(IV)/g, 26.0 (S0), 25.6 (S1) mg Pd(II)/g resin, where S1 – the multifunctional system, S0 – the single component system (static method) and 0.92 mmol Au(III)/g, 0.66 mmol Pt(IV)/g, 0.9 Pd(II) mmol/g dry resin (dynamic method). Desorption of Au(III), Pt(IV) and Pd(II) ions from the resin was made using a 5 % thiourea solution in 0.1 M hydrochloric acid with the yield 98, 97 and 98%.
The studies of the use of the ion exchanger Metalfix Chelamine of tetraethylenepentamine ligands (1,4,7,10,13 – pentaazatridecane) in the process of recovery, concentration and separation of platinum metal ions, gold and their accompanying elements from the environmental samples, anodic sludges from the electrorefining of copper ores, spent car exhaust gas catalysts, etc. [93–98].
Polyorgs type chelating ion exchangers [58, 99–103] are used for separation, concentration and removal of palladium(II) ions and other noble metals from deposits, rocks, ores, minerals and industrial waste waters. The Polyorgs sorbents were prepared by introducing e.g. imidazole, pirazole, mercaptobenzothiazole, amidooxime groups to the macroporous copolymers (polystyrene, polyvinyl, polyacrylonitrile) and other matrices. Sorbents of this type are characterized by high chemicals stability in strong acid and alkaline solutions as well as high thermal resistance and can be applied in the whole pH range. The sorbents of Polyorgs type (11-n, 15-n, 17-n and 33-n) were also used for filling fibres e.g. polyacrylonitrile (PAN), cellulose, polyvinyl (PVA) ones. In the literature, such sorbents are called filled fibrous sorbents (FFS) [99, 102, 103]. Main advantages of FFS are good kinetics of sorption and ease in their separation from solution which make them more attractive than sorbents in the form of powder or grains.
Recovery of palladium ions from chloride and chloride-nitrate(V) solutions using the ion exchanger Amberlite IRC-718 of functional iminodiacetate groups and polystyrene skeleton was conducted by Hubicki et al. [104]. The largest total ion exchange capacities of Amberlite IRC-718 were obtained in the 0.1M HCl (1.099 mmol/g) and 0.9M HCl–0.1M HNO3 (0.693 mmol/g) solution. The additional of 1M AlCl3, 1M CuCl2 or 1M NiCl2 results in significant drop of ion exchange capacity.
Studies of Amberlite IRC-718 selectivity towards Pd(II), Pt(IV) and Au(III), Ti(IV), Ag(I), Al(III), Co(II) and Fe(III) were carried out also by Park and co-workers [105]. The optimal sorption conditions for Pd(II), Pt(IV) and Au(III) ions are pH = 0.1–4 and a flow rate ≤ 2 cm3/min. Quantitative desorption of noble metal ions was conducted using 20 cm3 of 0.25 M thiourea and a flow rate 1 cm3/min. The ion exchange capacity of the studied ion exchanger was 0.34 mmol Pt(IV)/g; 0.69 mmol Au(III)/g and 0.55 mmol Pd(II)/g of the resin. From a practical point of view, the chelating ion exchanger Amberlite IRC-718 can find application in removal, concentration and separation of noble metal ions from the solutions originating from hydrometallurgical processing of car exhaust gas catalysts, anodic sludges, wastewaters as well as in removal and determination of gold(III) ions in printed computer plates PCP [105].
Of special importance are the studies by Sanchez et al. [106–109] of building triisobutylphosphine sulfide (TIBPS, Cyanex 471X) into the styrene-divinylbezene (4% DVB) copolymer in order to obtain a resin concentrating noble metal ions. Polymers are characterized by high selectivity towards Au(III) and Pd(II) ions (sorption from chloride solutions) as well as a lack of selectivity towards Ir(IV), Rh(III), Pt(IV) and Fe(III), Cu(II) or Ni(II) [106]. Based on the obtained values of sorption capacities (mmol/g) towards Pd(II) ions, the affinity series of the studied resins is as follows: Pd(II): Polymer 2 (0.07 mmol/g) < Polymer 1 (0.11 mmol/g) < Polymer 5 (0.17 mmol/g) < Polymer 3 (0.51 mmol/g) < Polymer 4 (0.72 mmol/g) [106].
With the temperature increase in the range 298–333K, there is observed the increase in Au(III) ions sorption compared to that of Pd(II) ions. The sodium nitrate(III) and thiourea solutions were used as eluents. Sodium nitrate(III) (2 M, pH 4.7) desorbs 75% of Pd(II) practically not washing out Au(III) from the ion exchanger, whereas thiourea (0.5 M, [H+] 0.1 M) enables almost quantitative recovery of gold(III) containing trace amounts of palladium (II) ions.
Kałędowski and Trochimczuk [110, 111] synthesized polymers containing calixpyroles preparing among others the resin B4 (covalently bonded thiophene kalix[4]pyrol[2] with the vinylbenzene chloride and divinylbenzene (VBC-DV, 0.5% DVB) of the expanded gel structure) selective towards noble metal ions. The maximal sorption capacity values determined from the Langmuir adsorption isotherms are 0.26 mmol/g; 0.55 mmol/g; 0.6 mmol/g; 0.61 mmol/g and about 1.7 mmol/g for Ag(I), Pt(II), Pt(IV), Pd(II) and Au(III), respectively. The resin B4 can be applied for the selective removal of Au(III) from the solutions originating from processing of ores, galvanic sludges containing other noble metals. The metals adsorbed on the resin are quantitatively washed out using 2 M solution of HCl or 2 M HNO3-Pt(IV), 0.5 M thiourea + 0.1 M HCl-Ag(I) and 5% solution of KCN-Au(III). In the case of palladium(II), the recovery was not quantitative (>57%, 0.5M thiourea in 0.1M HCl).
Garcia et al. [112] used the polystyrene-based resin of 15-membered triolefinic azamacrocycle rings in Pd(II) and Pt(IV) ions sorption from aqueous and aqueous dioxane solutions. The addition of dioxane (10% v/v) results in increasing polymer swelling and effectiveness of palladium(II) ions sorption from 48% to 73%. The total sorption capacities for Pd(II) and Pt(IV) ions were 0.36 mmol/g and 0.28 mmol/g of the resin, respectively. The presence of Cu(II) and Ni(II) ions affects insignificantly the selectivity of the resin towards noble metals. 0.5 M thiourea in 0.1 M HCl was used as an eluent of Pd(II) and Pt(IV) ions with 100% and 79% recovery, respectively.
Chen and Zhao [113] prepared the chelating resin PAN-ATAL by immobilization of cross-linked polyacrylnitrile (PAN) (7% DVB) with 2-amino-2-thiazole (ATAL) selective towards noble metals, i.e Pd(II), Ru(II), Ir(IV) and Rh(III) ions, for which the sorption capacity values were 230.7 mg Pd(II)/g, 147.1 mg Ir(IV)/g, 137.6 mg Ru(IV)/g and 72.1 mg Rh(III)/g of the resin. The affinity of chelating macroporous resin PS-BMT (where PS – the cross-linked chlorometylated polystyrene (10% DVB), BMT – 2,5-dimercapto-1,3,4-thiadiazole) for Pd(II), Au(III) and Pt(IV) ions from chloride solutions was studied by Qu et al. [114]. The sorption capacity for Au(III) ions 5.8 mmol/g is much higher than for Pd(II) ions 0.19 mmol/g and Pt(IV) ions 0.033 mmol/g which is associated with gold(III) chlorocomplexes coordination by two donor N and S atoms of the resin and reduction of gold(III) to a metallic form. However, in the case of PdCl42- and PtCl62- complexes, only one donor atom – sulfur atom takes part in bonding.
It is worth presenting also the studies of using chelating fibres for the removal of platinum elements, for example, those Gong [115] and Li et al. [116] on application of fibres of functional imidazole groups in noble metal ions sorption. Bilba et al. [117] used chelating polyacrylamidoxime fibres in concentration and recovery of Pd(II) ions from chloride solutions. The attention should be also paid to the investigation by Gong and Wang [118, 119] as well as Chang et al. [120] on concentration of trace amounts of Au(III), Pd(II), Pt(IV) and Ir(IV) by means of chelating polyacrylacylaminothiourea fibres. Poly (acrylamidrazonehydrazide) [121] and poly (acryl-p toluenesulfonamideamidine-p-toluenesulfonylamide) [122] fibres were applied in quantitative concentration and separation of Au(III) and Pd(II) as well as Ru(III), Rh(III), Au(III) and Pd(IV) ions in the column system.
Of a large group of ion exchangers, anion exchangers of different basicity (strong, average and weak basic) of functional groups are applied in ion exchange chromatography of noble metal ions. Strongly basic anion exchangers possessing well-dissociated functional groups capable of anion exchange of even weak acids, e.g. quaternary ammonium groups, are widely applied in the whole pH range. This group includes types 1 and 2 strongly basic anion exchangers of functional trimethylammonium groups (type 1) and dimethylhydroxyethylammonium groups (type 2). Weakly basic anion exchangers possess poorly dissociated functional groups i.e. primary-, secondary- and tertiary amine groups. There is also a group of amphoteric ion exchangers which, depending on solution pH, are able to exchange anions or cations. They are polyacids and polybases so-called polyampholites, e.g. of COO- and –N+(CH3)3 groups (snake in cage polymers).
Application of amphoteric ion exchangers for removal of trace amounts of Pd(II), Pt(IV) and Au(III) ions, among others, geological materials was studied by Chajduk-Maleszewska and Dybczyński [123], Dybczyński et al. [124] and Samczyński et al. [125] and Hubicki et al. [104]. Duolite ES 346 containing the functional amidoxime groups was successfully applied for recovery and separation of noble metal ions. There was proved high selectivity of amphoteric ion exchange Duolite ES 346 in Pd(II) ions sorption from the chloride (0.1–6M HCl–0.0011M Pd(II) and chloride-nitrate(V) (0.1–0.9 M HCl–0.9–0.1M HNO3–0.0011M Pd(II)) systems.The total sorption capacity towards Pd(II) ions is 1.099 mmol/g (0.1 M HCl) and 1.545 mmol/g (0.1M HCl–0.9M HNO3). The processes of sorption and separation of trace amounts of Pd(II), Au(III) and Pt(IV) from ammonium and aqueous-non-aqueous solutions on Duolite ES 346 were also conducted [123, 124]. Also high selectivity of this ion exchanger towards noble metal ions was proved. Ions desorption was achieved using the solutions: 2 M HCl (elution of Pt and other metal ions, 8 M NH4OH–0.01 M NH4Cl-CH3OH (1:5), desorption temperature 323 K (elution of Au(III) and 0.3 M CS(NH2)2 in 2 M HNO3 (elution of Pd(II)).
The amphoteric vinylpiridine ion exchangers VP-14K, ANKF-5 and the anion exchanger AN-251M were used for recovery of Pd(II) ions from spent car exhaust gas convertors subjected to extraction with the NaCl (2–2.3 M) solution acidified with hydrochloric acid (0.5–2 M) at 353 K, the extraction time was 4h. These ion exchangers were characterized by high affinity towards palladium(II) ions and their recovery was 98–99%. The sorption capacity of the anion exchanger AN-251M towards Pd(II) ions and the aminophosphonic ion exchanger ANKF-5 was comparable (2.4-2.5 mmol/g) and much larger than that of the ion exchanger VP-14K (1.4 mmol/g) so the ion exchangers AN-251M and ANKF-5 can be recommended for this type of application.
The strongly basic gel anion exchanger Dowex 1x10 (Cl- form, grain size 100-200 mesh) was successfully applied for removal of Pd(II) and Pt(IV) ions from the dust collected in Germany from street and fast traffic roads (Saarbrücken, motorway A-1, A-61, road B-262). Quantitative desorption of sorbed metal ions took place using the 0.1 M thiourea solution in 0.1 M HCl at the increased temperature 333 K enabling reduction of the eluent volume by half. The matrix ions, i.e. Cd, Cu and Fe, were not retained on the anion exchanger but Ni, Pb and Zn sorbed at 8–15 %. Elimination of interferences during noble metals determination was achieved by using the reagents masking the matrix ions even before the sorption process, e.g. xylene orange (C31H32N2Na4O13S) [126]. Application of ion exchange technique for the determination of platinum(II) ions in biological tissues gives interesting results. The tissues with the cis-dichloro-diamineplatinum(II) were irradiated with neutron in the reactor. The sample irradiation was mineralized by means of HNO3-H2SO4-H2O2 mixture. Then platinum ions were sorbed on the anion exchanger Dowex 1x8 in the chloride form with 6 M hydrochloric acid solution. Platinum was determined using the radiometric method [127]. Platinum and rhodium contained in ores were determined after separation on the anion exchanger Dowex 1x8 in the chloride form. The ore was digested in
For removal and determination of platinum from geological materials, a technique using the anion exchanger Rexyn 201 was proposed. Sorption was performed from 0.5 M of hydrochloric acid solution containing Ir(IV), Pt(IV), Pd(II) and Au(III) ions. Elution was carried out by means of 0.1 M solution of thiourea in 0.1 M HCl. Ir(III) was eluted using 6 M HCl. Platinum metals and gold were determined radiometrically [129]. The same methods were applied for the determination of platinum in carbons [130]. Somewhat modified technique was used for the determination of platinum metals in meteorites. Modification consisted in the change of the anion exchanger Rexyn 201 on Deacidite FF in the chloride form [131].
Bio-Rad AG1x8 (100–200 mesh) was characterized by high selectivity for Pd(II), Pt(IV) and Au(III) ions (the partition coefficient values were 106, 104, 103 for Au(III), Pt(IV) and Pd(II) ions, respectively), and therefore it could be applied for removal of noble metal ions from the environmental and geological samples, among others, from rocks, ores as well as dust and road dust [132].
Similar studies of application of anion exchangers Amberlite IRA-900 (macroporous, polystyrene, strongly basic anion exchanger of type 1, 16–50 mesh) [133–135] and Amberlite IRA-410 (gel, polystyrene, strongly basic of type 2, 16–50 mesh) [135] for recovery and removal of trace amounts of Pd(II), Pt(II), Ru(III), Rh(III), Au(III) and Ir(IV) ions from chloride and radioactive nitrate waste waters were carried out by the Els et al. [133, 134] and El-Said et al. [135]. Selectivity of the anion exchanger Amberlite IRA–900 for Pd(II) ions depends on the concentration of Clˉ ions in the solution. Quantitative sorption of palladium(II) ions from the chloride solutions is obtained at [Clˉ < 0.25 M. Sorption capacity of the anion exchanger Amberlite IRA-900 for Pd(II) ions in 0.2 M HCl solution was 0.0017 mmol/dm3 ([Pd2+] 350 ppm) [133]. Selectivity of the anion exchanger Amberlite IRA-900 towards noble metal ions changes in the series:
Satisfactory results were obtained using the above-mentioned anion exchanger for separation of Pd(II) and Ni(II), Sr(II), Rh(III), Eu(III), Ce(III), Ru(III), U(VI), Fe(III), Cr(III), Al(III), Ca(II) and Cs(I) from the radioactive nitrate waste waters [135].
The anion exchangers of quaternary ammonium groups: Purolite A-850 and Amberlite IRA-958 of polyacrylate skeleton, Lewatit MP 500A of polystyrene-divinylbenzene skeleton as well as Varion AP of functional pyridine groups and polystyrene-divinylbenzene skeleton exhibit high selectivity for Pd(II) ions from chloride and chloride-nitrate(V) solutions. Sorption capacities towards Pd(II) ions are 0.0282 g/cm3 (in 0.1 M HCl) and 0.0005 g/cm3 (in 6 M HCl) for Amberlite IRA-958 as well as 0.0408 g/cm3 (in 0.1 M HCl) and 0.005 g/cm3 (in 6 M HCl) for Purolite A-850. The addition of Zn(II) and Al(III) to the solution largely decreases selectivity of most anion exchangers for Pd(II) ions. The exception is Varion AP, whose selectivity changes insignificantly despite the presence of Al(III) ions [136, 137].
Due to modification of the macroporous polystyrene-divinylbenzene resin Amberlite XAD-1, the ion exchanger containing functional tertiary amine groups was obtained. This ion exchanger was used for separation of noble metal ions. Separation of Rh(III), Pd(II) and Pt(IV) ions mixture was achieved using suitable eluents:
Rh(III) – 1M HCl or 1M NaCl in 0.1 M HCl
Pd(II) – 0.05 M NaClO4 in 1 M HCl or 1 M NaCl + 0.025 M NaClO4
Pt(IV) – 0.1 M NaClO4 in 1 M HCl or 1 M NaCl + 0.15 M NaClO4.
The method is quick (about 30–40 minutes) and allows separation of 1.18–11.8 μg amounts of noble metal ions [138].
Among weakly basic anion exchangers of special interest is the macroporous polystyrene-divinylbenzene anion exchanger of functional dimethylamine groups Amberlite-93 used for recovery of Pd(II), Pt(II) and Rh(III) ions from spent car exhaust gas convertors. Rhodium(III) was desorbed from the anion exchanger as the first using 6 M hydrochloric acid solution, then palladium(II) was desorbed using 1% ammonia solution at room temperature. Platinum(II) was washed out with the ammonia solution of the concentration 5% (at increased temperature). Separation of palladium from platinum from the eluant solution can be achieved reducing to the metallic form or precipitating (NH4)2PdCl4 and (NH4)2PtCl6 using hydrochloric acid. The presented method of selective removal of platinum metals using Amberlite IRA-93 can be regarded as an effective technique for separation of these ions on a laboratory and commercial scale [139].
The weakly basic Amberlite IRA 67 is applied for selective removal of microquantities of platinum(IV) ions from the acid solution containing CuCl2, FeCl3, NiCl2, AlCl3 and ZnCl2. In chloride solutions, the above components can partly form anions, which reduces the sorption capacity of weakly basic anion exchangers. The effect of the above-mentioned macrocomponents on decrease of sorption capacity towards platinum(IV) ions can be presented in the series: CuCl2 ≈ FeCl3 ≈ NiCl2 < AlCl3 < ZnCl2 [140, 141]. A similar series can be determined for the anion exchanger Duolite S 37, which contains secondary and tertiary functional groups added to the phenol-formaldehyde skeleton [142].
In the literature, there are many examples of the alternative sorbents for noble metals removal produced from renewable and low-cost resources [143]. Among them, those based on bacteria, fungi and algae as well as agriculture and seafood wastes (coffee, green tea, tea, yuzu, aloe, wheat and barley straw, maize crop, coconut shell, rise husk, etc.) have been investigated. One of the low-cost sorbents is chitosan (CS) [144-155]. It is a kind of abundant natural polysaccharide. Chitosan is produced by the alkaline deacetylation of chitin, the most abundant biopolymer in nature after cellulose. It is extracted from shrimp and crab shells. Due to large availability of functional groups such as amino and hydroxyl ones, CS has been proved to be very efficient for the recovery of several toxic metal ions such as Cu(II), Cd(II) and Pb(II) and strategic metal ions such as Pt(IV) and Pd(II) [144]. It should be mentioned that sorption properties of CS are due to its composition and presence of active and functional groups. CS is characterized by its high percentage of nitrogen present in the form of amine groups, which are responsible for metal ion binding through chelation mechanisms. Due to the fact that it is protonated in acidic solutions, it is also capable of sorbing metal ions through anion exchange mechanisms. It should be mentioned that chitosan protonation in acidic solution causes the polymer to dissolve (except in sulphuric(VI) acid solutions). For the sorption of some metal ions (for example noble metals), sulphuric(VI) acid cannot be used for pH control due to reduction of sorption efficiency [145].
In the case of chitosan derivatives obtained by glutaraldehyde cross-linking (GA), poly(ethyleneimine) grafting through glutaraldehyde linkage (PEI) or thiourea grafting (T), noble metal ions can be sorbed. The reasons for grafting new functional groups are (i) to increase the density of sorption sites, (ii) to change the pH range for metal ions sorption and (iii) to change the sorption sites and/or the uptake mechanism in order to increase sorption selectivity for the noble metals [146]. Such derivatives were used for palladium and platinum removal [147]. It was found that the maximum adsorption capacity occurred at pH 2.0 for both Pt(IV) and Pd(II) species. The material selectively adsorbs Pt(IV) and Pd(II) from binary mixtures with Cu(II), Pb(II), Cd(II), Zn(II), Ca(II) and Mg(II). The isotherm adsorption equilibrium was well described by the Langmuir isotherms with the maximum adsorption capacity of 129.9 mg/g for Pt(IV) and 112.4 mg/g for Pd(II), which was relatively high compared with the glycine chitosan derivative (122 mg/g for Pt(IV) and 120 mg/g for Pd(II)). The results show that 0.5 M EDTA-0.5 M H2SO4 solution can effectively desorb Pt(IV) and Pd(II) (>97%) metal ions from the adsorbent material. The high percentage of desorption obtained when the 0.5 M EDTA–0.5 M H2SO4 solution was used and can be explained by both stable complexes and the electrostatic interactions between the Pt(IV) and Pd(II) species.
In the paper [143], rubeanic acid was grafted on chitosan through the reaction with glutaraldehyde as the linker to obtain the sorbent for Au(III) with the thiol functional groups. It was found that the maximum sorption capacity was high and equal to 600 Au(III) mg/g. The speciation of gold in the chloride and hydroxide chloride systems appears to be a predominant parameter influencing the removal process. The optimum pH range was between 2 and 3 for glutaraldehyde cross-linked chitosan. However, the sorption capacity strongly decreases with the increasing pH. It was found that in the case of the grafting of sulfur compounds on chitosan derivatives, the partial change in the sorption mechanism occurs. In this case, metal ion chelation with sulfur compounds is weakly sensitive to the pH change [148]. Sorption capacity in the HCl system reaches 2 mmol/g (180 mg/g) and is slightly lower than for the chitosan derivatives obtained by grafting of pyridyl groups (6 mmol/g). Increasing chloride concentration involves a significant decrease in sorption capacity.
The removal of Au(III), Pt(IV) and Pd(II) onto the glycine modified cross-linked chitosan resin was investigated in the paper by Ramesh et al. [146]. The results show that the optimum pH appeared to be 1.0–4.0, and the maximum percentage removal was obtained at pH 2.0 for Au(III), Pt(IV) and Pd(II). The pHZPC was found to be 5.1. At pH < pHPZC, the surface of modified chitosan resin is positively charged, whereas at a pH > pHPZC, the surface of modified chitosan resin is negatively charged. Due to the positive surface charge of sorbent at pH lower than pHPZC, it attracts the chlorocomplexes of platinum, palladium and gold, resulting in the greater amounts of adsorption at low pH. The authors proposed the following mechanism of the sorption process:
The results also demonstrated that the amount of adsorption was decreased with the increasing chloride ion concentration. This is because of strong interaction between the chloride ions and precious metal ions to form chlorocomplexes. The 0.7 M thiourea-2 M HCl solution was the most effective for the desorption of Au(III), Pt(IV) and Pd(II).
In the case of chitosan derivatives, noble metal ions are sorbed according to several kinetic models based on pure sorption, pure reduction and dual sorption-reduction mechanisms [149, 150]. Moreover, the optimum acid pH for noble metal ions sorption depends on the metal. For platinum and palladium, it was equal to 2. For CS cross-linked by glutaraldehyde (CS-GA) for hydrochloric acid solutions of palladium at pH 2, sorption reached the same level as achieved at pH 1 (capacity strongly decreased) [151]. However, in the sulphuric(VI) acid solutions, the sorption capacity remains almost unchanged. It is well known that pH has a critical effect on the speciation of the metal in solution because the distribution of metal species depends on pH. Other parameters which affect the sorption efficiency are connected with the nature of the sorbent (ionic charge), chemistry of the metal ion: ionic charge, ability to be hydrolysed as well as metal concentration and the composition of the solution and the form of polynuclear species [151]. Sorption kinetics is controlled by particle size, cross-linking ratio and palladium concentration. In hydrochloric acid solutions, equilibrium is achieved at 24 h contact. For chitosan-cellulose fibres, it was found that incorporation of cellulose fibres improves the binding efficiency of chitosan towards Ag(I). The sorption capacity was close to 220 mg/g. This is much higher than for the pure chitosan (140 mg/g) [152]. The cellulose fibres contribute to dispersion of the chitosan chains that are more accessible and available for silver. It is also possible to modify the chitosan structure by introducing cross-linking structure, blending chitosan with synthetic polymers such as poly(vinyl alcohol) (PVA) – a non-toxic, water-soluble synthetic polymer with good physical and chemical properties and film-forming ability. It is also possible to apply the sol-gel process to develop organic–inorganic hybrid materials [153–155]. For this aim, clays and silicas are frequently used. Clays are composed of silicate layers which form three-dimensional structures after hydrated in water. They have negative charge and can interact with chitosan. Also silicas are characterized by several advantages which are among others surface stability in the acidic medium and highly developed surface, acceptable kinetics, thermal stability, resistance to microbial attack and low cost should be mentioned [156]. Chemically modified silicas (CMSs) with the functional groups covalently bound to the surface such as polyamines, particularly, linear polyhexamethylene guanidine (PHMG) with convenient amine group configurations and nitroso-R salt (NRS) were used in palladium sorption [157, 158]. Complex of palladium(II) with the ratio Pd:NRS = 1:2 formed the SiO2–PHMG–NRS. The other examples are presented in Table 2.
\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t\t\n\t\t\t\t | \n\t\t
Thiosemicarbazide | \n\t\t\tPd(II) | \n\t\t\t[159] | \n\t\t
Dithizone | \n\t\t\tAg(I) | \n\t\t\t[160] | \n\t\t
2-Amino-1-cyclopentene-1-dithiocarboxylic acid | \n\t\t\tAg(I) and Pd(II) | \n\t\t\t[161] | \n\t\t
N-(3-triethoxysilylpropyl)-4,5-dihydroimidazoleuene | \n\t\t\tPd(II), Pt(II) | \n\t\t\t[162] | \n\t\t
Amidinothiourea | \n\t\t\tAg(I), Au(III) and Pd(II) | \n\t\t\t[162] | \n\t\t
3-(1-thioureido)propyl | \n\t\t\tAg(I), Au(III) and Pd(II) | \n\t\t\t[163] | \n\t\t
Organofunctionalized silicas in pre-concentration of noble metal ions.
Ion exchange has been widely applied in the technology of chemical separation of noble metal ions. This is associated with the dissemination of methods using various ion exchange resins which are indispensable in many fields of chemical industry. Due to small amounts of noble metals in nature and constant impoverishment of their natural sources, of particular importance are physicochemical methods of their recovery from the secondary sources as well as waste waters.
Recovery of noble metals, from such raw materials, requires individual approach to each material and application of selective methods for their removal. Moreover, separation of noble metals, particularly platinum metals and gold from geological samples, industrial products and synthetic mixtures along with other elements, is a problem of significant importance nowadays.
Spinocerebellar ataxia (SCA), which is included in spinocerebellar degeneration (SCD), is a genetically heterogeneous group of autosomal dominantly inherited progressive disorders [1]. Cerebellar atrophy is the most prominent clinical feature of this condition and is accompanied by spinal cord and sequential brain stem and basal ganglion damage. Therefore, coordinated movement of the eyes, head, trunk, and extremities is impaired. Therefore, the activities of daily living (ADL) and participation in social activities are limited, and the quality of life (QOL) is undisputedly impaired in these patients [2].
The effects of medication and surgery in this clinical setting depend on the cause of ataxia and the extent of neuronal damage [3, 4]; however, there is no rational effective treatment for SCA and it is difficult to slow the progression of the disease. Rehabilitation [5, 6], including physical therapy [7, 8], aimed at improving/maintaining motor function, ADL, and QOL [5] is an important intervention for patients with SCA. Here we provide a narrative review of physical rehabilitation for SCA.
For the clinical diagnosis of cerebellar ataxia, specific blood studies and magnetic resonance imaging (MRI) have been performed [9]. Furthermore, genetic techniques improve the diagnosis of degenerative cerebellar ataxia [10]. Although the details of the findings of these genetic and blood studies are beyond the scope of this review of rehabilitation, cerebellar atrophy and cerebellar motor deficits are traditionally common observations in patients with degenerative cerebellar ataxia [9]. Furthermore, recently, the absence of motor cerebellar symptoms has also been recognized as being important for rehabilitation [11].
The cerebellum is the motor-control system in humans [12]. Clinically, the oculomotor deficit, speech deficits, ataxia in the trunk and extremities, balance disorder, and gait disturbance are the targets of rehabilitation in SCA [9, 13]. The possible underlying pathogenetic mechanisms include distorted timing, abnormal sensory acquisition, impaired sensory motor synchronization, impaired triggering of corticomotor excitability, and abnormal visuokinesthetic cerebro-cerebellar interactions [13].
Oculomotor deficits cause deoptimized vision. The vestibulo-ocular reflex and smooth pursuit [14] partially depend on motor prediction in static and dynamic movement and contribute to dynamic gazing [15]; moreover, the cerebellum contributes to the trainability of eye-head coordinated movements [16].
Abnormal excitability and modulation in the motor cortex and corticospinal tract causes a voluntary contraction deficit in [17, 18]. Cerebellar stimulation modulates the motor-evoked potential induced by transcranial magnetic stimulation (TMS) of the primary motor cortex [19, 20, 21]; however, this modulation is absent in patients with SCA [22, 23]. Furthermore, the cortical silent period, which reflects the excitability of the inhibitory GABAergic neural circuit in the primary motor cortex, is abnormal in these patients [24, 25, 26, 27, 28, 29], and this cerebellar effect on the cortical silent period is characteristic of the healthy population [30]. Before muscle contraction for movement, the corticospinal excitability increases in healthy individuals; in contrast, this facilitation is insufficient in SCA [31]. In addition, in patients with SCA, muscle tones are decreased [11] and the spinal reflex excitability is facilitated by cerebellar stimulation [32, 33, 34]. The long latency spinal reflex, which is correlated with the cortical circuit, is disturbed in SCA [35]. Although this functional cerebellum-spine connection may contribute to the preparation for muscle contraction, there is insufficient evidence that these connections contribute to motor control in healthy and cerebellar ataxia populations.
In simple movements, such as extension of the elbow, coordinated activity of the biceps and triceps is needed. For ballistic elbow-extension movement practice, the triphasic muscle agonist and antagonist contraction patterns contribute to the smooth movement, but under/overshooting appears during the uncoordinated contraction pattern of patients with SCA [36, 37]. Furthermore, this contraction pattern may be obtained by temporal electrical stimulation in these individuals [37].
The cerebellar internal model contributes to predictable/online/offline motor control and motor learning/adaptation [38]. The symptoms associated with motor learning do not appear at the onset of the cerebral atrophy [39], because several brain areas, i.e., the prefrontal cortex, primary motor cortex, and basal ganglia, compensate for cerebellar function in early-stage SCA [5, 6, 39]. Recently, the motor learning deficit at the early stage of the disorder was reportedly detected using an adaptation task [40]. Therefore, the assessment of the capacity for motor learning may be important to strategize the interventions that are concretely described in the following sections.
Representative nonataxia symptoms include hyperreflexia, areflexia, extensor plantar, spasticity, paresis, muscle atrophy, fasciculations, myoclonus, rigidity, chorea/dyskinesia, dystonia, resting tremor, sensory symptoms, urinary dysfunction, cognitive impairment, and brain stem oculomotor signs [41]. The Inventory of NonAtaxia Symptoms (INAS) [41] is used to estimate these nonataxia symptoms. The appearance of these symptoms depends on the type of SCA [41].
We should conduct assessment to detect the degree of motor dysfunction and consider more effective intervention of physical rehabilitation. The first, the imaging technology such as MRI provides us with structural information about the atrophic areas of the brain associated with the disease. We described about neuroimaging technique in Section 3.1. The next, we can use some outcome measurement to estimate the motor dysfunction and verification in the physical rehabilitation. Then, we introduce the representable outcome measures for physical rehabilitation in SCA in Section 3.2. However, we had not established method to estimate the remaining of motor learning ability, which is one of the most important factors to predict the effect of physical rehabilitation. Therefore, we propose the possible assessment of motor learning ability in Section 3.3.
Neuroimaging is a technique that is used to visualize the structural and functional activities of the brain. MRI measurements, such as diffusion tensor imaging and surface-based morphometry, visualize the brain structures. Functional activity imaging is achieved using fMRI and NIRS, which are indicators of cerebral blood flow, and electroencephalogram (EEG) and magnetoencephalography, which are indicators of electrical activity. Positron emission tomography and single-photon emission computed tomography with nuclear tracers are also used in this setting. The application of neuroimaging in the rehabilitation of cerebellar disorders includes voxel-based lesion symptom mapping in patients with stroke, to investigate the recovery of upper arm reach [42] and walking ability [43] depending on the lesion site.
Although conventional MRI [44] is widely used for the neuroimaging of spinocerebellar degeneration, to obtain diagnostic findings, few studies have used neuroimaging as a guideline or outcome of rehabilitation. The lack of reports in this context hampers the quantification of cerebellar degeneration in SCA and its correlation with motor dysfunctions. In terms of measurement techniques, the cerebellum exhibits a much tighter folding compared with the cerebral cortex, with individual cortical sheets with a thickness of 1–2 mm and a sheet area of 1500–2000 cm2, compared with a sheet area of 2200 cm2 with a thickness of 1.5–4 mm in the cerebral cortex. Therefore, the typical 2–4 mm3 spatial resolution of neuroimaging techniques is insufficient to capture local cerebellar changes. Patient factors include the difficulty in limiting the brain regions involved in movement disorders to the cerebellum, because the degenerative regions in SCD extend beyond this structure to multiple brain regions [45].
Among the neuroimaging modalities, the role of voxel-based morphometry (VBM) is notable in SCA rehabilitation. VBM is a statistical analysis of the entire brain in voxel units (1 mm3) that is used to identify the behavioral patterns and related brain morphological characteristics of patients [46]. Burciu et al. assessed the degree of cerebellar atrophy concerning motor and learning functions using VBM to evaluate brain structure changes after 2 weeks of balance training in patients with SCD; these authors reported the association between an increased volume of the dorsal premotor cortex and increased balance ability [47]. Matsgi et al. reported an association between VBM and neurophysiological markers in cerebellar brain inhibition (CBI), with atrophy of the dentate nucleus at VBM observed in cases of pure cerebellar ataxia that did not show CBI [48]. Bando et al. reported a correlation between adaptive learning ability and gray matter volume of the cerebellar IV-VII lobules and the supramarginal gyrus in a prismatic adaptation task in SCA [49]. Thus, VBM may be a biomarker to explain motor dysfunction in patients with SCA.
Conversely, VBM is not an ideal tool to show a causal relationship between brain structural changes and behavioral differences. As a solution to this problem, we can propose a combination of VBM and neurostimulation [50], as neurostimulation of the brain regions associated with the behavioral patterns obtained by VBM and the observation of behavioral changes before and after stimulation allow us to examine brain degeneration sites and behavior.
Gait disturbance is a major symptom of the cerebellar pathology in SCA [51]. The functional ambulation categories (FAC) is useful for the comprehensive assessment of walking ability; the FAC assesses gait for about 15 m and climbing stairs and classifies gait levels into 6 levels [52]. The FAC is also used in the exercise program created by Research Committee for Ataxia Disease (Research team under the jurisdiction of the Ministry of Health, Labour and Welfare in Japan, http://ataxia.umin.ne.jp/rehabilitation/).
The quantitative assessment of cerebellar ataxia is very important in clinical practice. The International Cooperative Ataxia Rating Scale (ICARS) has been used as a quantitative assessment of ataxia symptoms. However, it has been noted that the test reliability of the eye movement items is low [53]. The Scale for Assessment and Rating of Ataxia (SARA) is an 8-item performance-based scale that yields a total score of 0–40 (most severe ataxia). The minimal detectable change (MDC) for individual score difference from the baseline to the 1-year follow-up in SARA was <3.5 (n = 171; SCA1, n = 43; SCA2, n = 61; SCA3, n = 37; and SCA6, n = 30; mean age, 50.9 ± 13.5 years; mean disease duration, 11.8 ± 5.6 years) [54]. SARA does not include an eye movement section. Schmahmann et al. noted the importance of assessing oculomotor abnormalities and developed the Brief Ataxia Rating Scale, a modification of ICARS [55]. Each SCA genotype exhibits specific symptoms [56]. Therefore, these assessments should be used differently for different symptoms. However, one feature that is consistent among these assessments is that the scoring range is large and does not allow the assessment of minute symptom changes. Honda et al. developed a system to measure the evaluation of SARA using a depth sensor [57]. Using this system, the degree of ataxia can be measured numerically. In addition, because the system is inexpensive, it can be installed at the patient’s home, making it a useful tool for telemedicine.
The balance dysfunction in SCA has a significant impact on QOL [58]. The Berg Balance Scale and the Timed Up and Go test are widely used to assess balance dysfunction in SCA [59]. However, despite their widespread use, these assessments have not been examined for reliability and validity in SCA. Kondo et al. examined the test reliability of the Balance Evaluation Systems Test (BESTest) [60]. The BESTest is a multitask balance assessment tool that was developed to identify specific postural control problems (i.e., biomechanical constraints, stability limits, anticipatory postural adjustments, postural responses, sensory orientation, dynamic balance during gait, and cognitive effects) [61]. The MDC for an individual score difference from the baseline to the 4-week follow-up in BESTest was <8.7 (n = 20; SCA3, n = 4; SCA6, n = 9; SCA31, n = 7; mean age, 63.7 ± 10.1 years; age at onset, 53.9 ± 10.5 years; baseline SARA, 9.9 ± 3.5) [61]. Many types of balance function measures have been reported. However, BESTest is the only scale that is considered to have absolute reliability in SCA.
Gait speed is often used as an outcome of intervention studies in SCA [62, 63]. However, some changes in the gait pattern (e.g., base of support and gait speed) most likely reflect cerebellar-unspecific, compensatory strategies, and a high spatiotemporal gait variability appears to be a distinctive feature of ataxic gait [58, 64]. The Gait Variability Index (GVI) is a measure of gait variability that has been examined regarding reliability and validity [65]. The MDC for an individual score difference from day 1 to day 2 in GVI was <8.6 (Friedreich’s ataxia, n = 81; baseline ICARS, 70.4 ± 7.9) [65]. It has been suggested that gait instability in SCA are characterized by a stronger effect of balance-related impairments of cerebellar control during slow walking and a stronger effect of impaired intra-limb coordination during fast walking [58]. Therefore, in clinical practice, it is necessary to evaluate not only the optimal gait speed, but also slow walking and fast walking, to extract the characteristics of gait instability.
The cerebellum has the ability to compensate for tissue damage and loss of function. This is called the cerebellar reserve [6]. Mitoma et al. suggested that this is important for motor rehabilitation at a time when the cerebellar reserve is functioning [6]. Motor rehabilitation in the early stages may maintain and improve the cerebellar reserve [66, 67]. Therefore, it is important to assess this parameter.
Cerebellar ataxia is the main symptom of SCA. Ataxia symptoms may represent a compensation for predictive control using feedback control [6]. Predictive control requires a mechanism called internal model [38]. The internal model is constantly updated by motor learning [68]. In turn, motor learning is one of the most important functions of the cerebellum. Thus, a measure of motor learning ability may be useful as an assessment of the cerebellar reserve.
Prism adaptation (PA) is widely used as an assessment of motor learning ability in patients with SCA [40, 69]. The basic procedure of PA is shown in Figure 1. First, at the “baseline,” the task is performed without a prism lens. Subsequently, the prism lens is introduced and the task is performed. In the initial phase, the lens is set off to either the left or right side of the target, but the error is corrected as the number of repetitions increases. This period is called the “initial error correction phase.” Thereafter, a spatial realignment phase is performed under the prism lens. The purpose of this phase is to gather visuospatial information including the errors. Next, the prism is removed and an “after-effect phase” is performed. If the spatial information is being re-learned, errors are generated in the opposite direction to the initial error correction phase. Recently, Hashimoto et al. developed the Adaptability Index (AI), which is a composite index computed from several parameters measured PA (Figure 2). The clinical efficacy of the AI in discriminating patients with SCA from healthy individuals has been demonstrated [70]. Furthermore, Bando et al. found that a reduced AI was correlated with gray matter atrophy in the cerebellum in the SCA group [49]. In particular, the right lobule VI and the left Crus I showed the most robust correlation. These cerebellar regions are consistent with the correlates of PA detected in previous human and nonhuman primate studies [71, 72]. AI is considered as a motor learning index that reflects the cerebellar reserve (in this case, the degree of cerebellar atrophy).
Overview of prism adaptation. The ordinate shows the finger-touch error represented from the target to the touch point. Three phases are generally used: (1) absence of a prism lens (prism off), (2) presence of a prism lens (prism on), and (3) absence of a prism lens (prism off).
Calculation of the adaptability index (AI). The AI is calculated as follows: AI = a × b × c, where “a” is the adaptation index defined as the probability of correct touches in the last 10 trials of the spatial realignment phase 1, “b” is the retention index defined as the probability of incorrect touches in the initial 5 trials of the after-effect phase, and “c” is the extinction index designated as the probability of correct touches in the last 10 trials of the spatial realignment phase 2.
PA can be implemented using a simple system. In addition, it takes only 20 min to complete a PA. Reaching tasks can be performed even in the period during which the patient is unable to walk, and the fact that the PA can be assessed continuously over a long period is an advantage. However, only cross-sectional studies have been conducted in previous reports [40, 49, 69, 70, 73, 74]. Future studies need to be designed to examine long-term changes and intervention effects.
The targets of rehabilitation in cerebellar ataxia are mainly disability in ADL, gait, and motor dysfunction. Therefore, GAS, FIM, 10-m walking test, TCA, SARA, ICARS, and BESTest are used as important outcomes in rehabilitation. The most important strategies of rehabilitation for cerebellar ataxia including SCA consists in balance training (see Section 4.3), gait training (see Section 4.2), and muscle strengthening training using a high-intensity program (see Section 4.1). Further, optional possible interventions are using assistive technology (see Section 4.4) and neuromodulation technique (see Section 4.5).
Rehabilitation methods for cerebellar ataxia have been reported [75]. The most important strategy is the increase in the intensity of physical training, such as balancing, gait, and strength [76]. Several systematic reviews [77, 78, 79] and narrative reviews [3, 75, 80, 81] introduced and recommended intensive physical therapy for cerebellar ataxia in patients with SCA. Miyai et al. [62] reported that physical and occupational therapies of 2 h × 5 days +1 h × 2 days per week for 4 weeks were applied to inpatients and improved the SARA score and gait speed; however, the effect was carried over only up to 12 weeks after the training, and had disappeared at 24 weeks [62]. Conversely, Ilg et al. reported that intensive coordinative physiotherapy delivered over 4 weeks improved motor performance in degenerative cerebellar ataxia in a study with an intraindividual control design [63].
An outpatient rehabilitation program for 6 weeks applied to 19 participants with Friedreich’s ataxia improved the motor domain item in the FIM score and Friedreich’s Ataxia Impact Scale, but the posthome program could not maintain the effect [82]. Therefore, this finding indicates that continuous outpatient rehabilitation programs are important for maintaining the ADL in patients with Friedreich’s ataxia. Additional large-scale studies are needed to investigate the long-term effect of outpatient rehabilitation programs and identify the characteristics of patients who respond to treatment. Therefore, the development of optimal individual programs is important to obtain the effect of training, regardless of the inpatient, outpatient, or home-self-training setting [83]. The semi-order program of the Research Committee for Ataxia Disease (Research team under the jurisdiction of the Ministry of Health, Labour and Welfare in Japan, http://ataxia.umin.ne.jp/rehabilitation/) can be used for this purpose.
Subsequently, the continuity of the intensive training is an important factor, because degradation in physical function was reported. Therefore, approaches aimed at upkeeping these programs in a way that suits the patients are needed. For example, exergames contribute to the practice of exercise at home. In the future, tele-rehabilitation systems [84] should be tested for the improvement (or maintenance) of the function and continuity of exercise.
Gait training has been reported to improve spatiotemporal gait parameters (cadence, step length/width, gait speed, etc.) [85, 86, 87], complex gait (Timed Up and Go test, Dynamic Gait Index) [85], independence (FAC) [86], ataxia (SARA) [88], and adaptive locomotor adjustments (ALA) [88]. Patients with SCA exhibit problems other than the gait disturbance itself, i.e., stiffening of the body in an attempt to avoid the occurrence of gait disturbances. Therefore, it is important to focus on gait disturbances and increasing the number of walking patterns when considering gait training in a person with SCA.
Disturbances of gait are the core features of SCA [89, 90, 91, 92], thus leading to a risk of falling down [93]. Patients with cerebellar ataxia walk with a reduced walking speed and cadence, as well as reduced step length, stride length, and swing phase; increased walking base width, stride time, step time, stance phase, and double limb support phase; and increased variability of step length, stride length, and stride time [94]. These items are affected by both balance-related impairments and deficits related to limb control and intra-limb coordination [95]. We believe that balance training and coordination training are key to the improvement of gait disturbances. Regarding the details of balance training, please refer to the Section 4.3.
In addition, stiffening of the body leads to a decrease in the number of walking patterns; as a result, ALA deteriorates [96, 97]. ALA implies that obstacle avoidance is achieved by modifying basic walking patterns in response to obstacle properties, e.g., a sloping road, stepping over an obstacle, or dynamically changing the spaces created by pedestrians in a hallway. In persons with SCA, feelings of anxiety as a result of the frequent experience of falls, as well as deficits related to limb control by ataxia, could negatively affect their ALA because of increased muscular co-contractions and reduced joint movements [98]. We will describe the approaches to improve ALA in the next paragraph.
The proposals for gait training are as follows: gait training without or with a treadmill. First, in gait training without a treadmill, we refer the reader to Section VI of the BESTest as gait adaptability training [61]. Section VI of the BESTest consists of a 7-item scale: (1) Gait Natural, (2) Change Speed, (3) Head Turns, (4) Pivot Turn, (5) Obstacles, (6) “Get Up & Go” Test, and (7) Cognitive Task “Get Up & Go” Test, aimed at evaluating the stability of the gait. These elements are important to improve ALA. As an example of gait training, persons with SCA are asked to walk while making an effort to change their walking speed according to therapist’s instructions to engage is “fast (or slow)” walking as fast (or slow) as possible. If patients need assistance when walking, you might want to change the walking speed with the support of a therapist.
Second, gait training using a treadmill has advantages in that patients can practice a relatively large amount of gait training over a short period and the therapists can control the speed and incline easily. Gait training using a treadmill has been reported as a potentially promising tool for improving ALA in a person with SCA [88], as well as gait disturbances in a person with Parkinson’s disease [99, 100]. It has been reported that variability was increased during slow and fast walking, but was normal during the preferred walking speed in a person with cerebellar ataxia [101]. Another study reported that, in ataxia, walking at the preferred speed minimizes the gait abnormalities, and the analysis of gait at a wide range of speeds is recommended [94]. For this reason, when using a treadmill in gait training, we suggest that walking be practiced at the speed at which the gait disturbance increases (i.e., slow or fast walking speed) for specific patients. When the fear of falling increases, the use of a harness is recommended, to provide a safe environment for gait without the fear of falling.
It is important to improve the balance ability and ALA during gait training in a person with SCA. Gait training is a relatively easy method; however, it is left to the therapist’s discretion and experience. By changing the task itself or adjusting the difficulty level of the task, gait training may be able to overcome the limited walking patterns of these patients.
All patients with SCA will develop balance difficulties during the course of the disease. Balance is essential for mobility, and is very important for QOL. Although there is no effective pharmacological treatment for decreasing the ataxia or slowing disease progression, physical therapy plays an important role in controlling ataxia and improving or maintaining function through training [76]. In general, the physical therapy programs for degenerative cerebellar ataxia are based on intensive static and dynamic balance and coordination training. There is some evidence that such therapeutic training programs alleviate the ataxic symptoms and improve functional activities in a person with cerebellar ataxia [63, 78, 102, 103]. In these patients, the disease progressively damages the cerebellar structure that plays a crucial role in motor learning [104]; however, these studies have indicated that it is necessary for highly repetitive balance training for balance impairment in SCA. For this reason, highly repetitive balance training in patients with SCA should be the focus of future studies.
More concretely, balance training exercises in early stages of the disease, i.e., ambulation, include the following categories: (1) static balance training, (2) dynamic balance training, and (3) coordination training (Figure 3). In addition, combining a dual task with balance training improves balance and reduces the number of falls in individuals with cerebellar ataxia [105].
National Center of Neurology and Psychiatry (NCNP) balance training program. This balance training program was devised through consultations with patients with SCA, medical doctors, and therapists at the NCNP in Japan. In the advanced stage of SCA, it is recommended to perform the programs indicated by an asterisk.
Moreover, it is important to provide support for these approaches and make them a habit of exercising. For instance, if the patients with SCA have no habit of exercising, they should start with a small number of exercises (i.e., the minimum necessary) to get used to exercising, followed by the gradual increase in the number of exercises. If the patients with SCA have a habit of exercising, the therapist should teach them to adjust the exercise load (e.g., exercise more slowly and/or provide a small base of support). It is also important to adopt balance training that can be enjoyed, e.g., video games [106] and Tai Chi [107], as a means of continuing balance training.
In advanced stages of the disease (i.e., no ambulation), it is necessary to perform balance training under safe conditions (e.g., prone, supine, crawl, and sitting positions), to prevent the decrease in physical activity. Even in advanced stages, it has been reported that a person with degenerative ataxia may benefit from balance training [108]. In addition, it is necessary to focus on ADL and living infrastructure at this stage. If a patient with SCA requires assistance during transfer, engaging in repetitive transfer training with assistance and/or modification of the living infrastructure (e.g., installation of handrails) are necessary.
Focusing on highly repetitive balance training in patients with SCA might preserve the balance function. There is no scientific basis for the number of balance training exercises that are necessary to achieve this goal; however, we would like to recommend engaging in 30 repetitions at least per balance training session. Furthermore, the balance training must be designed to provide a significant challenge to the person’s balance. If a person with SCA wants to preserve the balance function, they have to continue engaging in repetitive balance training, “use it or lose it.” However, few studies have reported the effect of gait and balance training in persons with SCA. Therefore, further studies are needed to clarify the clinical effectiveness of gait and/or balance training.
In recent years, various technologies have been used in the assessment of and treatment based on rehabilitation, as well as to support daily life in patients with SCD. Curara, a wearable robotic system, assists both hip and knee movements and supports the wearer’s rhythmic gait using a synchronization control based on a central pattern generator [109]. Gait support using the curara system has been reported to improve gait smoothness in patients with SCD [110]. In addition to these findings, a recent study addressed the effects of robotic gait training combined with noninvasive brain stimulation. This report showed that robot gait training using Lokomat-Pro in combination with cerebellar tDCS improved the functional scores on SARA, especially the scores on the subitems of gait, stance, sitting, and heel-shin slide compared with robot gait training alone [111]. Thus, hybrid training using robots and noninvasive brain stimulation will be applied to the rehabilitation treatment of patients with SCD in the future.
Accordingly, the use of walking aids is a complementary method for balance and gait impairment. In general, walking aids such as canes and walkers improve postural stability, but their improper use increases the risk of falling [112]. Because the manipulation of a cane requires coordinated upper limb movements [113], patients with SCD who have upper limb ataxia are likely to experience difficulty in using a cane. Conversely, because a walker does not require much coordinated movement of the upper limbs, technology-based walkers are being developed. Recently, a smart walker for mobility assistance and monitoring system aid, ASBGo, was developed and reported to improve gait parameters and postural stability in patients with SCA [114, 115]. In addition to technology, some studies on walking assistance using dogs and handkerchiefs have also been reported. Walking with a rehabilitation dog that has been specifically trained for goal-directed interventions or with an assistance dog that helps people with physical disability and mobility impairments has been reported to improve balance while walking in patients with SCD [116]. Furthermore, the handkerchief-guided gait, in which the patient with SCD walks along with the caregiver while maintaining light tension on a handkerchief by pulling lightly, has been shown to decrease body swaying and increase stride length and gait velocity during walking [117].
Moreover, technology is also being used as a tool to assess ataxia in patients with SCD living at home. Most of them represent attempts to evaluate SARA, which is a typical measure of ataxia, at home. In recent years, a technology aimed at objectively evaluating the speech, upper and lower limb, balance, and gait functions using wearable inertial sensors and a Kinect camera was developed, which makes it possible to discriminate between normal and abnormal functions and to detect ataxia at an early stage [118]. In addition, SaraHome has been developed to allow the remote evaluation of SARA items using Kinect and Leap Motion Controller [119]. Moreover, a spoon equipped with an inertial sensor, called Ataxia Instrumented Measurement-Spoon, has been developed, which allows the evaluation of upper limb function in ataxia while eating with a spoon [120, 121, 122]. Because SCD is an intractable neurological disease, it is difficult for many patients to leave their houses. Therefore, the contribution of technology to home-based rehabilitation is expected to increase in the future if a low-cost and easy method of assessing ataxia at home is established using the technologies and products of daily living described above.
Regarding the support of ADL, BMI studies have been reported. Patients with severe SCA often have difficulty in communicating because of language impairment. The application of BMI using event-related potentials and frequency bands of EEG is being investigated as a solution to this problem. The operational accuracy of BMI using P300 for event-related potentials was 82.9% in patients with SCA, which was similar to the accuracy observed in healthy subjects (83.2%) [123]. There are also reports of BMI manipulation in patients with SCD using the EEG frequency band associated with motor imagery [124]. BMI has a wide range of applications in diseases of the central nervous system, such as communication tools, transportation, and life support, and is expected to contribute to the QOL of patients with SCD.
Neuromodulation via noninvasive brain stimulation (NIBS) is a potential method for the treatment of cerebellar ataxia [19, 125]. A previous systematic review [126] reported the effectiveness of cerebellar neuromodulation using the TMS technique of transcranial direct current stimulation (tDCS). The SARA and ICARS scores in patients with SCA3, multiple system atrophy, and postlesion ataxia, as assessed using real cerebellar rTMS (1 Hz), were significantly lower than those detected in the sham stimulation group [126]. Furthermore, no harmful side effects were noted [126]. Cerebellar rTMS can modulate the plasticity of the vestibular reflex [16, 127]; therefore, cerebellar rTMS has potential for application in balance training to enhance vestibular contributions.
A single session of anodal cerebellar tDCS (2 mA, 20 min) significantly improved SARA, ICARS, 9-hole-peg test, and 8-m walking test scores [128]. Furthermore, combined anodal cerebellar tDCS and cathodal spinal DCS (5 days/week, 2 weeks) improved SARA score, ICARS score, 9-peg test, and 8-m walking time in patients with degenerative cerebellar ataxia [129]. There is insufficient evidence regarding whether simultaneous stimulation is more effective than single stimulation [130]; however, it is possible that this intervention method will produce improvements. Based on these findings, which were gleaned from small-sample studies, we suggest that a neuromodulation montage will improve the ataxia, balance, and gait ability. Therefore, we should perform further studies using a larger population.
Individualized physical rehabilitation programs for patients with SCA may improve/maintain their motor function, balance, gait ability, and ADL. In particular, the intensity and continuity of gait and balance training need to be considered to achieve effectiveness. Furthermore, several technologies, such as depth sensors, robotics, and NIBS, have contributed to the development of methods for the assessment and treatment of motor dysfunction in individuals with SCA. We should continue to study populations suffering from dysfunction caused by SCA.
This work was supported by Shijonawate Gakuen University and JSPS KAKENHI (Grant Number 20 K11298).
The authors declare no conflict of interest.
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On September, 29th 2006 he has won a post PhD fellowship from the university of Bologna (from October 2006 to October 2008), at the competitive examination he was ranked first in the industrial engineering area. He extensively served as referee for several international journals. He is author/coauthor of more than 100 research papers. He has been involved in some projects supported by MURST and European Community. 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After finishing his P. hD degree in 1992, he served in the Industry as a Scientific Officer and continued his academic career as a visiting scholar for a number of educational institutions. In 1996 he joined National University of Science & Technology Pakistan (NUST) as an Associate Professor; NUST is one of the top few universities in Pakistan. In 1999 he joined an International Company Lineo Inc, Canada as Manager Compiler Group, where he headed the group for developing Compiler Tool Chain and Porting of Operating Systems for the BLACKfin processor. The processor development was a joint venture by Intel and Analog Devices. In 2002 Lineo Inc., was taken over by another company, so he joined Aalborg University Denmark as an Assistant Professor.\nProfessor Akbar has truly a multi-disciplined career and he continued his legacy and making progress in many areas of his interests both in teaching and research. 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Biochemistry examines macromolecules - proteins, nucleic acids, carbohydrates, and lipids – and their building blocks, structures, functions, and interactions. Much of biochemistry is devoted to enzymes, proteins that catalyze chemical reactions, enzyme structures, mechanisms of action and their roles within cells. Biochemistry also studies small signaling molecules, coenzymes, inhibitors, vitamins, and hormones, which play roles in life processes. Biochemical experimentation, besides coopting classical chemistry methods, e.g., chromatography, adopted new techniques, e.g., X-ray diffraction, electron microscopy, NMR, radioisotopes, and developed sophisticated microbial genetic tools, e.g., auxotroph mutants and their revertants, fermentation, etc. More recently, biochemistry embraced the ‘big data’ omics systems. Initial biochemical studies have been exclusively analytic: dissecting, purifying, and examining individual components of a biological system; in the apt words of Efraim Racker (1913 –1991), “Don’t waste clean thinking on dirty enzymes.” Today, however, biochemistry is becoming more agglomerative and comprehensive, setting out to integrate and describe entirely particular biological systems. The ‘big data’ metabolomics can define the complement of small molecules, e.g., in a soil or biofilm sample; proteomics can distinguish all the comprising proteins, e.g., serum; metagenomics can identify all the genes in a complex environment, e.g., the bovine rumen. 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Dr. Blumenberg’s research is focused on the epidermis, expression of keratin genes, transcription profiling, keratinocyte differentiation, inflammatory diseases and cancers, and most recently the effects of the microbiome on the skin. 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In recent years, the application of chemistry to biological molecules has gained significant interest in medicinal and pharmacological studies. This topic will be devoted to understanding the interplay between biomolecules and chemical compounds, their structure and function, and their potential applications in related fields. Being a part of the biochemistry discipline, the ideas and concepts that have emerged from Chemical Biology have affected other related areas. 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Behind these definitions are hidden all the aspects of normal and pathological functioning of all processes that the topic ‘Metabolism’ will cover within the Biochemistry Series. 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Thus proteomics, an area of research that detects all protein forms expressed in an organism, including splice isoforms and post-translational modifications, is more suitable than genomics for a comprehensive understanding of the biochemical processes that govern life. The most common proteomics applications are currently in the clinical field for the identification, in a variety of biological matrices, of biomarkers for diagnosis and therapeutic intervention of disorders. From the comparison of proteomic profiles of control and disease or different physiological states, which may emerge, changes in protein expression can provide new insights into the roles played by some proteins in human pathologies. Understanding how proteins function and interact with each other is another goal of proteomics that makes this approach even more intriguing. Specialized technology and expertise are required to assess the proteome of any biological sample. Currently, proteomics relies mainly on mass spectrometry (MS) combined with electrophoretic (1 or 2-DE-MS) and/or chromatographic techniques (LC-MS/MS). MS is an excellent tool that has gained popularity in proteomics because of its ability to gather a complex body of information such as cataloging protein expression, identifying protein modification sites, and defining protein interactions. The Proteomics topic aims to attract contributions on all aspects of MS-based proteomics that, by pushing the boundaries of MS capabilities, may address biological problems that have not been resolved yet.",annualVolume:11414,isOpenForSubmission:!0,coverUrl:"https://cdn.intechopen.com/series_topics/covers/18.jpg",editor:{id:"200689",title:"Prof.",name:"Paolo",middleName:null,surname:"Iadarola",fullName:"Paolo Iadarola",profilePictureURL:"https://s3.us-east-1.amazonaws.com/intech-files/0030O00002bSCl8QAG/Profile_Picture_1623568118342",institutionString:null,institution:{name:"University of Pavia",institutionURL:null,country:{name:"Italy"}}},editorTwo:{id:"201414",title:"Dr.",name:"Simona",middleName:null,surname:"Viglio",fullName:"Simona Viglio",profilePictureURL:"https://s3.us-east-1.amazonaws.com/intech-files/0030O00002bRKDHQA4/Profile_Picture_1630402531487",institutionString:null,institution:{name:"University of Pavia",institutionURL:null,country:{name:"Italy"}}},editorThree:null,editorialBoard:[{id:"72288",title:"Dr.",name:"Arli Aditya",middleName:null,surname:"Parikesit",fullName:"Arli Aditya Parikesit",profilePictureURL:"https://mts.intechopen.com/storage/users/72288/images/system/72288.jpg",institutionString:null,institution:{name:"Indonesia International Institute for Life Sciences",institutionURL:null,country:{name:"Indonesia"}}},{id:"40928",title:"Dr.",name:"Cesar",middleName:null,surname:"Lopez-Camarillo",fullName:"Cesar Lopez-Camarillo",profilePictureURL:"https://mts.intechopen.com/storage/users/40928/images/3884_n.png",institutionString:null,institution:{name:"Universidad Autónoma de la Ciudad de México",institutionURL:null,country:{name:"Mexico"}}},{id:"81926",title:"Dr.",name:"Shymaa",middleName:null,surname:"Enany",fullName:"Shymaa Enany",profilePictureURL:"https://s3.us-east-1.amazonaws.com/intech-files/0030O00002bRqB9QAK/Profile_Picture_1626163237970",institutionString:null,institution:{name:"Suez Canal University",institutionURL:null,country:{name:"Egypt"}}}]}]}},libraryRecommendation:{success:null,errors:{},institutions:[]},route:{name:"profile.detail",path:"/profiles/428993",hash:"",query:{},params:{id:"428993"},fullPath:"/profiles/428993",meta:{},from:{name:null,path:"/",hash:"",query:{},params:{},fullPath:"/",meta:{}}}},function(){var e;(e=document.currentScript||document.scripts[document.scripts.length-1]).parentNode.removeChild(e)}()