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Venkateswarlu",coverURL:"https://cdn.intechopen.com/books/images_new/371.jpg",editedByType:"Edited by",editors:[{id:"58592",title:"Dr.",name:"Arun",surname:"Shanker",slug:"arun-shanker",fullName:"Arun Shanker"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"67138",title:"Using Wearable Devices in Educational Assessment: Smartphone Exams",doi:"10.5772/intechopen.84324",slug:"using-wearable-devices-in-educational-assessment-smartphone-exams",body:'\n
\n
1. Wearable technology
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Wearable technology is a group of devices that can be worn by people and track and communicate the colorful information with the outside world. The first known wearable computing device was invented in 1961 by MIT Edward Thorp and Claude Shannon, and the world’s first calculator wristwatch was released in 1975. Wearable technology specially Fitbit, smart watches, and smart phones is attracting more interest of many consumers in the finance, gaming, health, music fields, as well as educators specially after the 2010s. They are specially designed to address the majority of the population who are still inactive [1]. These devices can be integrated into clothing, recognizable personal accessories (glasses, contact lenses, and watches), or additional devices (pocket device to count steps) [2]. Revenues in this segment are forecast to grow even faster than unit shipments, more than tripling in value to over $32 billion by 2019 up from $10 billion in 2013 (see Figure 1) [3].
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Figure 1.
Global shipment and revenue market forecast for wearable technology [3].
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As wearable devices become smaller, inexpensive, and more feature packed, the opportunity for use in various applications grows alongside [4]. People have tactile and kinesthetic senses to feel the objects’ properties like its size, shape, weight (light or heavy), and temperature (hot or cold), and these ensures them about the existence and the reality. In this meaning, using wearable devices in education motivates students more than the other devices.
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2. Switch to wearable devices in education: smartphone case
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We are residing in a planet where technology is contemporary in our life routines. The achievement of personal goals of needs leads the individual to attain the activities voluntarily [5, 6, 7, 8] which is also necessary to achieve their goals [5, 9]. These lead to the result that students and their motivation are the most significant part of the achievement of our courses. In this sense, choosing the best technological device brings the best possible outcome!
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Today, smartphones are one of the vastest revolutions in individuals’ life spans. They give mobility and excitement to its users that these modern technological devices become the most significant part of many people’s lives. From online banking to watch the news on TV, we are confronting the progressions and affects that convey to our lives. The school could not stay out of these progressions, and a range of classrooms had been altered, from special spaces for the perusing of scholarly messages, to sight and sound spaces, where the utilization of data and correspondence innovation had accomplished incredible significance. Students of the twenty-first century prefer the lightest, the simplest, and the most popular way of communal and educational communication. They record everything in their smartphones for future use and are not volunteers for paper works.
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Lots of students at universities have smartphones and are using its facilities like taking pictures, recording videos, and using social media. According to eminent pedagogy expert Scott P. Simkins, as far as technological innovations are alarmed, it is not pedagogy itself that mattered, but how pedagogic innovation is exploited by taking into account the specific environment in which it is implemented [10]. In the educational model where education process is carried out fully or partially with mobile technologies, students use mobile devices in wireless environments and engage in formal and informal learning [11, 12, 13]. Mobile learning model is also differentiated from other learning models by its mobility [14]. Universities and institutions have been utilizing advances, for example, synchronous videoconferencing (SV), online courses, and other kinds of technological innovations to convey language courses for the part of their educational modules. This is an open door, which is constantly important to the quickly developing requirement for understudies to end up able in utilizing innovative applications and comprehend the part of learner-focused engagement in language learning [15]. With backing of such innovations, most of these language related courses have begun being delivered online. The use of mobile phone is very popular these days specially in language learning. Mobile devices helps language teachers to use a variety of teaching methods and techniques according to students’ different needs, interests, motivations and learning styles. While there have been many researches on using or integrating the mobile technology into language teaching in literature, very few of them is about the devices in wireless environments [11, 12]. The most important difference between mobile learning and other learning activities is that learners are continually on the move [14]. Universities and institutions have been utilizing advances, for example, synchronous videoconferencing (SV), online courses, and other kinds of technological innovations to convey language courses for the part of their educational modules. This is an open door, which is constantly important to the quickly developing requirement for understudies to end up able in utilizing innovative applications and comprehend the part of learner-focused engagement in language learning [15]. With backing of such innovations, most of these language-related courses have begun being delivered online. Nowadays, the use of mobile phone has received considerable attention in education as well as in language learning. Language teachers use a variety of teaching methods and techniques by considering students’ different needs, interests, motivations, learning styles, and strategies as well as their pace in learning. While there have been many researches on using or integrating the mobile technology into English language teaching in literature, very few of them dwell on the usefulness of smartphones as an assessment tool from students’ perspectives. Several studies have investigated the impact of mobile phones on learning outcomes in adult learning programs among rural populations and poor communities in developing countries [16, 17]; and some examined the use of mobile devices to support intentional informal learning among experienced users [18]. Ranieri and Bruni [19] stated that mobile phones are used for storytelling as well. Ranieri and Pachler [20] delivered a research study and collected data through formal and informal meetings, direct and indirect observations, interactions with participants, and focus groups and concluded in their research study that adults have great trust in the power of the media but were somewhat disappointed at their own lack of skills.
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Mobile education has been delivered to university students for decades, and lots of researchers have delivered researches to discuss its efficiency and students’ perspectives about it [21, 22, 23, 24, 25]. However, using mobile technologies like smartphones in education is relatively a new concept, and several educators and researchers start discussing this new technology in their reports [26, 27, 28, 29, 30]. There are lots of portable equipments like smartphones m-learning feasible at anytime and anyplace compared to the use of a notebook that can easily be damaged and does not last long [26, 27, 28]. Some research studies among Islamic education teachers are delivered for using mobile phones in secondary schools, and it is found that there is a potential for m-learning produced for Islamic education in secondary schools [29, 30].
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Mobile phones have been used to provide access to contextually relevant information in clinical education [31], to create digital narratives to be used in adult education [32], and as vehicles for interactive museum guidebooks [33]. There are also studies which have been focused on developing assistive, mobile, experiential language learning applications to enhance daily literacy education anywhere and at anytime [34, 35]. Some researchers stressed that mobile media are commonly exploited in both more and less conscious modes [36, 37, 38]. Jankovića [39] examined the simultaneous impact of Facebook and smartphone usage on leisure activities and college adjustment of students in Serbia. Rheea and Kimb [40] delivered a survey with a total of 450 workers in Korea to see if there were differences in the effects of breaks with smartphones (e.g., browsing the Internet or using social network services) which have a different association with “conventional breaks” (e.g., walking or chatting face-to-face with friends).
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3. Some problems on the way
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There are some obstacles in using mobile phones in education. Some of these are students not having smartphone, slow Internet access, and insufficient smartphone usage awareness. Also, administrators’, teachers’, and students’ negative attitude toward smartphone usage in education may present an obstacle in this new technology’s usage. Some research studies show that there was no significant difference between the traditional, blended, and mobile groups of students’ paper and mobile exam results [41]. Also, studies show that there is not a significant difference between male and female students’ exam results [41]. The only difference was between the students who were familiar with the mobile technology exams and between those who were novice.
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Students’ perspectives are vital guides for upcoming directions in teaching and learning [22]; therefore, research studies aimed first by finding students’ attitudes to smartphone usage; delivered education to three different groups of students to measure if there is any significant difference between students having mobile courses or other courses; and then the research is directed to students’ perspectives of mobile education. The increasingly widespread use of new communication methods via smartphones occupies an important place in the lives of young people and influences their leisure activities [39, 42]. A high percentage of students at universities have the latest technology smartphones and are professionals using its facilities like taking pictures, creating albums, and using Gmail, Viber, WhatsApp, and Facebook perfectly with their phones. Due to the reasonable price of mobile Internet connection plans, this usage increases day by day. Smartphones are today’s handheld computers for configuring the daily schedules, saving large documents, watching videos, listening music, using Internet, using World Wide Web, video conferencing, and much more than a human mind can imagine.
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There are also some researchers which state that using smartphones in a classroom is supported by data suggesting that the use of such technology (e.g., text messaging during class) is negatively related to sustained attention, and sustained attention itself is positively related to academic performance. On the other hand, the use of mobile technologies in the classroom also stimulates students while they learn new material [43]. Due to strong mobile technology infrastructure in communication and Internet connections, students can benefit from both formal and informal learning methods [44]. Sometimes, social media tools may not fit into the configurations of all mobile devices. Some of the functions may be disabled, and frequent update of software is required [45].
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4. Using wearable devices in assessment: mobile assessment
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Computer-assisted learning environments made use of branching based on learner interactions that were the same for all learners in that same situation [46], and mobile phone-assisted learning environments take learning a step forward. Mobile phones are being used in a variety of assessing purposes. Self-assessment and peer assessment can be meaningful forms of formative feedback [47]. It is critical to a teacher’s ability to adapt lessons and check for student understanding [48]. Using suitable technology for a successful implementation is important for assessing students’ performance about the key concepts related to the unit [49, 50], and in a current research, a new method of assessment via smartphones is used. Smartphone exams are being used in some universities for assessments. Figure 2 is a screenshot of two pages in an exam (the first page and the last page). In the exam, students and teachers were getting their results as soon as they finish the exam. This method claims to be the fastest method of assessing and evaluating students’ progress.
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Figure 2.
An exam with smartphones [41].
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5. A recent research with smartphones
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Three groups of students have attained to the smartphone exams at Cyprus Science University. The first group of students are the students who were liking coming to classroom and listening to teachers in the classroom. The second group of students were preferring to come to some of the courses and to follow the other courses from mobile technologies. The third group of students were mostly working and were not able to come to class; therefore, they were following the courses from their smartphones. This research is based on a qualitative research design that meanings, perceptions, and awareness of the prospective teachers have a potential impact to retrieve the qualitative findings within an inductive process.
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Seventy-five volunteer students who enrolled English I course in Guidance and Psychological Counseling program became part of this research. Volunteer participation provided a ground for confidentiality and trustworthiness within the process. In this research, trustworthy mobile phones and mobile exam programs were used as instrument tools. The mobile exam questions were distributed to students on the exam time. Students who took the exam and teachers who were the invigilators during smartphone exams had been given special training about how to use smartphones and how to access to the mobile exam via smartphones. Therefore, there were not any problems with the usage of smartphones.
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At the end of mobile exams, the average scores of mobile and paper exams were compared, and students’ results were driven from these comparisons. Blended course students’ English paper exam results (M = 87.76; SD = 12.81) were higher than the English mobile course students’ English paper exam results (M = 84.48; SD = 14.44), which was higher than the traditional course students’ paper exam results (M = 83.24; SD = 14.60). Traditional course students’ English mobile exam results (M = 73; SD = 16.46) is higher than the blended course students’ English mobile exam results (M = 72.60; SD = 23.14), which is slightly higher than the mobile course students’ English mobile exam results (M = 72.53; SD = 19.28). These results can be seen in Table 1.
\n
\n
\n
\n
\n
\n
\n
\n\n
\n
\n
N
\n
Mean
\n
Std. deviation
\n
Std. error
\n
\n\n\n
\n
English paper exams
\n
Traditional
\n
25
\n
83.24
\n
14.60
\n
2.92
\n
\n
\n
Blended
\n
25
\n
87.76
\n
12.81
\n
2.57
\n
\n
\n
Mobile
\n
25
\n
84.48
\n
14.44
\n
2.89
\n
\n
\n
Total
\n
75
\n
85.16
\n
13.96
\n
1.60
\n
\n
\n
English mobile exams
\n
Traditional
\n
25
\n
73.00
\n
16.46
\n
3.29
\n
\n
\n
Blended
\n
25
\n
72.60
\n
23.14
\n
4.63
\n
\n
\n
Mobile
\n
25
\n
72.00
\n
18.43
\n
3.69
\n
\n
\n
Total
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75
\n
72.53
\n
19.28
\n
2.27
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\n\n
Table 1.
English paper exams and English mobile exams.
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Students had English paper exams in three different classes: traditional, blended, and mobile. There was a normal distribution between the marks and an equal number in three groups; one-way ANOVA was used to check if there was a meaningful difference between these three groups. According to the results of this test, there was not a significant difference between the three groups of F(2, 72) = 1.86, p = 0.16. The achievement of students in traditional, blended, and mobile classes in English mobile exams was also calculated statistically. There was not meaningful significant difference between three groups on F(2, 72) = 0.53, p = 0.95 (see Table 2).
\n
\n
\n
\n
\n
\n
\n
\n
\n\n
\n
\n
\n
Sum of squares
\n
Df
\n
Mean square
\n
F
\n
Sig.
\n
\n\n\n
\n
English paper exams
\n
Between groups
\n
706.16
\n
2
\n
353.080
\n
1863
\n
0.163
\n
\n
\n
Within groups
\n
13643.92
\n
72
\n
189.499
\n
\n
\n
\n
\n
Total
\n
14350.08
\n
74
\n
\n
\n
\n
\n
\n
English mobile exams
\n
Between groups
\n
40.67
\n
2
\n
20.33
\n
0.053
\n
0.948
\n
\n
\n
Within groups
\n
27478.00
\n
72
\n
381.64
\n
\n
\n
\n
\n
Total
\n
27518.67
\n
74
\n
\n
\n
\n
\n\n
Table 2.
One-way ANOVA results for English paper exams and English mobile exams.
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These results can be interpreted as mobile exams which are also possible in education, and it’s just a choice of the examiners whether they want to make paper exams or mobile exams.
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Paper exam results of the two courses are used to make comparisons. In these comparisons, students belonging to three different groups are taken into consideration.
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Blended course students’ English paper exam results (M = 87.76; SD = 12.84), which are higher than the mobile course students’ English paper exam results (M = 84.48; SD = 14.44), are higher than the English paper exam results of traditional class (M = 83.24; SD = 14.60).
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Traditional course students’ computer paper exam results (M = 94.44; SD = 5.88) are higher than the blended course students’ computer paper exam results (M = 89.04; SD = 11.17), which are slightly higher than the mobile course students’ computer paper exam results (M = 86.76; SD = 14.23). These results can be seen in Table 3.
\n
\n
\n
\n
\n
\n
\n
\n\n
\n
\n
\n
N
\n
Mean
\n
Std. deviation
\n
Std. error
\n
\n\n\n
\n
English paper exams
\n
Traditional
\n
25
\n
83.24
\n
14.60
\n
2.92
\n
\n
\n
Blended
\n
25
\n
87.76
\n
12.84
\n
2.57
\n
\n
\n
Mobile
\n
25
\n
84.48
\n
14.44
\n
2.89
\n
\n
\n
Total
\n
75
\n
85.16
\n
13.93
\n
1.61
\n
\n
\n
Computer paper exams
\n
Traditional
\n
25
\n
94.44
\n
5.88
\n
1.18
\n
\n
\n
Blended
\n
25
\n
89.04
\n
11.17
\n
2.23
\n
\n
\n
Mobile
\n
25
\n
86.76
\n
14.23
\n
2.85
\n
\n
\n
Total
\n
75
\n
90.08
\n
11.31
\n
1.30
\n
\n\n
Table 3.
English and computer paper exams.
\n
Blended course students’ English paper exam results and traditional course students’ computer paper exam results were the highest among the students’ groups.
\n
A one-way ANOVA was conducted to compare the English paper exam results and computer paper exam results of traditional, blended, and mobile groups of students. There was a significant effect of three groups of F(2, 72) = 0.70, p = 0.50 in English paper exams as well as computer paper exams.
Although there was a meaningful difference in paper exams of computer and English courses; there was not any significant difference in their mobile exams as it can be seen in Table 5.
\n
\n
\n
\n
\n
\n
\n
\n
\n\n
\n
\n
\n
Sum of squares
\n
Df
\n
Mean square
\n
F
\n
Sig.
\n
\n\n\n
\n
Computer mobile exams
\n
Between groups
\n
60.67
\n
2
\n
30.33
\n
0.24
\n
0.784
\n
\n
\n
Within groups
\n
8939.00
\n
72
\n
124.15
\n
\n
\n
\n
\n
Total
\n
8999.67
\n
74
\n
\n
\n
\n
\n
\n
English mobile exams
\n
Between groups
\n
40.67
\n
2
\n
20.33
\n
0.053
\n
0.948
\n
\n
\n
Within groups
\n
27478.00
\n
72
\n
381.64
\n
\n
\n
\n
\n
Total
\n
27518.67
\n
74
\n
\n
\n
\n
\n\n
Table 5.
One-way ANOVA results for computer mobile and English mobile exams.
\n
Three groups of students have attained to mobile, blended, and traditional courses for 3 months. Results of the questionnaires bring out the conclusion of compatibility and standardization. The results show that students are as good at paper exams as they are at mobile exams. Therefore, we can conclude that smartphones can be used as assessment tools in mobile English exams and the choice does not affect the students’ success at the end-of-course exams. This gives a huge flexibility to the courses and freedom to teachers and students. The positive side of using smartphones is for teachers, who do not need to grade numbers of exam papers at the end of each exam. Neither should they have huge amounts of papers for examinations; thus, they save time and money. When we integrate mobile learning environments into our classrooms, teachers are required to know how to use and support that technology [51]. This may be a negative side in a smartphone usage for some teachers. Some of the limitations of this study are that it assumes that there is not an effect of sex on the results and it is restricted only with 75 first form psychology department students. Further studies about this can also be delivered to measure effect of mobile exams on other courses and with different groups of students.
\n
This research was significant in its own ways of research and its findings; and it aims to compare the success of students in English paper exams and English mobile exams, as well as discussing smartphone pros and cons as assessment tools.
\n
\n
5.1 Internet access problems
\n
From the previous experiences, it was observed that there were Internet accessibility problems when all the students tried to access the exam at the same time. Therefore, students are divided into groups and entered the exam. Even with smaller groups, it was observed that the questions were emerging slowly. By increasing the speed of Internet access, this problem was elevated.
\n
\n
\n
5.2 Print screen and copy problems
\n
Mostly, students had tried to find a way to cheat or to disobey the given rules; and they tested the programs by their own ways. They tried to take screenshots of the program, and this was prevented successfully. The students who tried to do this were warned by the course teacher. One student tried to shade the questions and cheat; this was also successfully prevented by displaying him a warning message.
\n
\n
\n
5.3 Translation problems
\n
The exam started when the teacher had made an active link on the Internet. Since the students used translation programs in their daily lives, their smartphones instantly converted the exam to the students’ native language, which was a critical problem for a language exam. Technicians corrected the problem quickly; however, it was a nasty thing. There are several possible solutions to this problem: additional codes can be included to the exam software to prevent such a case; the software can be distributed to students offline and can be programmed to send the results to the teachers’ smartphone. Another possible solution to this may be instead of distributing exam papers to the students, teachers can distribute smartphones with restricted facilities to students, and they can collect these at the end of the exams to be used for future exams.
\n
\n
\n
\n
6. Wearable devices in future
\n
We are residing in a planet where technology is contemporary in our life routines. The more that you know, the more that you want to know! Knowledgeable people are generally more keen on learning new technological devices. People’s relatively high rates of prior experience with computers and smartphones may partially explain the sample’s high willingness to accept smart wearable devices [4]. Today, smartphones are one of the vastest revolutions in individuals’ life spans. Smartphones are becoming increasingly popular, both in formal and informal educational environments. Although benefits and obstacles in using smartphones as assessment tools can be discussed, “70 percent of students and teachers agree that they prefer to write work and notes on their computers rather than writing on paper” [52], and recent studies shows that students are as successful in smartphone exams as they are in written exams.
\n
There are different students with different social needs: some are keen on being virtually social, and some are keen on being physically social (see Figure 3). Some research studies show that the younger physically social students are more successful than the younger virtually social ones [53, 54]; a solution to these would be improving wearable technologies in a way that students can both be physically and virtually social!
\n
Figure 3.
Physically virtual and virtually social [53, 54].
\n
\n\n',keywords:"mobile exam, students, English exam, assessments, success",chapterPDFUrl:"https://cdn.intechopen.com/pdfs/67138.pdf",chapterXML:"https://mts.intechopen.com/source/xml/67138.xml",downloadPdfUrl:"/chapter/pdf-download/67138",previewPdfUrl:"/chapter/pdf-preview/67138",totalDownloads:752,totalViews:0,totalCrossrefCites:1,totalDimensionsCites:1,totalAltmetricsMentions:0,impactScore:0,impactScorePercentile:41,impactScoreQuartile:2,hasAltmetrics:0,dateSubmitted:"October 26th 2018",dateReviewed:"January 10th 2019",datePrePublished:"November 12th 2019",datePublished:"December 4th 2019",dateFinished:"May 14th 2019",readingETA:"0",abstract:"We are residing in a planet where technology is contemporary in our life routines. Today, smartphones are one of the vastest revolutions in individuals’ lifespans. Smartphones are becoming increasingly popular, both in formal and informal educational environments. This chapter discusses the benefits and obstacles in using smartphones as an assessment tools and it compares the achievement of exams delivered via smart phones to paper-based exams. The result of the study indicates that; there was a significant difference between three groups of English Paper Exams, however there was not any significant difference between these groups on English Language Mobile Exams.",reviewType:"peer-reviewed",bibtexUrl:"/chapter/bibtex/67138",risUrl:"/chapter/ris/67138",book:{id:"7654",slug:"wearable-devices-the-big-wave-of-innovation"},signatures:"Oytun Sözüdoğru and Nazime Tuncay",authors:[{id:"216663",title:"Dr.",name:"Oytun",middleName:null,surname:"Sözüdoğru",fullName:"Oytun Sözüdoğru",slug:"oytun-sozudogru",email:"oytunsozudogru@gmail.com",position:null,profilePictureURL:"https://s3.us-east-1.amazonaws.com/intech-files/0030O00002bSEaNQAW/Profile_Picture_2022-06-08T10:53:15.jpg",institution:null},{id:"282309",title:"Dr.",name:"Nazime",middleName:null,surname:"Tuncay",fullName:"Nazime Tuncay",slug:"nazime-tuncay",email:"nazime.tuncay@gmail.com",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",institution:null}],sections:[{id:"sec_1",title:"1. Wearable technology",level:"1"},{id:"sec_2",title:"2. Switch to wearable devices in education: smartphone case",level:"1"},{id:"sec_3",title:"3. Some problems on the way",level:"1"},{id:"sec_4",title:"4. Using wearable devices in assessment: mobile assessment",level:"1"},{id:"sec_5",title:"5. A recent research with smartphones",level:"1"},{id:"sec_5_2",title:"5.1 Internet access problems",level:"2"},{id:"sec_6_2",title:"5.2 Print screen and copy problems",level:"2"},{id:"sec_7_2",title:"5.3 Translation problems",level:"2"},{id:"sec_9",title:"6. Wearable devices in future",level:"1"}],chapterReferences:[{id:"B1",body:'Noah A, Spierer DK, Gu J, Bronner S. Comparison of steps and energy expenditure assessment in adults of Fitbit Tracker and Ultra to the Actical and indirect calorimetry. Journal of Medical Engineering & Technology. 2013;7(7):456-462. Available from: https://www.ncbi.nlm.nih.gov/pubmed/24007317\n\n'},{id:"B2",body:'Shantz JAS, Veillette C. 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Ankara: Çözüm Educational Publishing; 2018\n'}],footnotes:[],contributors:[{corresp:"yes",contributorFullName:"Oytun Sözüdoğru",address:"oytun.sozudogru@adakent.edu.tr",affiliation:'
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1. Introduction
Ruthenium is a precious metal that belongs to the platinum-group elements [1]. As ruthenium can adopt various oxidation numbers, its coordination complexes adopt a wide variety of oxidation states from -II to VIII [2]. When nitrogen-based donor ligands are coordinated to a central ruthenium atom, the resulting ruthenium complexes generally prefer the +II and + III oxidation states, but occasionally also adopt the +IV and + V states. Arguably the most studied Ru complexes with nitrogen-based donor ligands are those that contain the hexaammineruthenium dication, [Ru(NH3)6]2+, and the tris(2,2′-bipyridine)ruthenium(II) dication, [Ru(bpy)3]2+(bpy = 2,2′-bipyridine) [3, 4, 5, 6]. [Ru(bpy)3]2+ was first reported by Burstall [7] and is easily obtained from the reaction of RuCl3•nH2O with an excess amount of bpy in aqueous ethanol. [Ru(bpy)3]2+ exhibits a stable low-spin t2g6 electronic configuration as well as a reversible one-electron oxidation at +1.29 V (vs SCE) and successive one-electron reductions at −1.33 V, −1.52 V, −1.76 V, and − 2.4 V vs. SCE; the oxidation is a Ru(II/III) metal-center-based process, while the reductions occur on the bpy ligands. [Ru(bpy)3]2+ exhibits a metal-to-ligand charge transfer (MLCT) band at 452 nm and bright luminescence at 612 nm (lifetime: 600 ns) under MLCT excitation. This luminescence arises from the triplet MLCT photoexcited state, which allows this complex to serve as a photosensitizer for a wide scope of photoenergy conversion processes and as a photocatalyst for organic transformations [8]. Therefore, it is hardly surprising that during the past five decades, numerous studies on photoactive [Ru(bpy)3]2+ complexes have been reported [3]. The tuning of their physical properties, such as their absorption/emission maxima or redox potential, via ligand modification has been achieved by introducing substituents on bpy or by replacing the bpy ligand with other N-heteroaromatic ligands. This tuning has led to a wide range of functional materials based on [Ru(bpy)3]2+.
For example, replacing one of the bpy ligands in [Ru(bpy)3]2+ with an N-heteroaromatic ligand comprising a benzimidazole and a pyridine group shifts the Ru(II/III) oxidation potential in negative direction because benzimidazole is a stronger σ-donor and weaker π-acceptor than pyridine [9]. Furthermore, the coordinated benzimidazole N–H imino group acts as a Brønsted acid, and the corresponding deprotonated benzimidazolate site can coordinate to another metal ion (Figure 1) [10]. Protonated or N-alkyl benzimidazolium ions can act as precursors for N-heterocyclic carbene (NHC) metal complexes [11, 12]. The representative pyridine-containing ligands 2,2′-bipyridine (bpy) and 2,2′,2″-terpyridine (tpy) form chelate complexes with bidentate and tridentate coordination modes. When one or two pyridine groups are replaced with benzimidazole, the resulting bidentate- and tridentate-coordinating ligands are known as 2-(2-pyridyl)benzimidazole and 2,6-bis(benzimidazol-2-yl)pyridine, respectively (Figure 2) [13, 14].
Figure 1.
Coordination modes of pyridine and benzimidazole as ligands.
Figure 2.
Chemical structures of bidentate and tridentate ligands that contain pyridine and benzimidazole group(s).
This chapter focuses on the molecular design of ruthenium complexes with N-heteroaromatic ligands, particularly benzimidazole derivatives. In Ru–benzimidazole complexes in aqueous solution, the solution pH strongly affects the Ru(II/III) oxidation potential, which is derived from the proton-coupled electron transfer (PCET) reaction in solution [15]. The proton-responsiveness of Ru–benzimidazole complexes has been exploited to obtain switching functionality in multinuclear Ru complexes [16, 17]. In addition, ligand modification via N-alkylation of the benzimidazole N–H imino group has been used to achieve the anchoring of redox-active Ru complexes [18, 19]. and the layer-by-layer (LbL) assembly of Ru complexes on indium-tin oxide (ITO) surfaces toward molecular electronic devices [20, 21, 22]. Figure 3 presents a schematic illustration of our conceptual approach for molecular devices based on surface-confined Ru complexes with electron/proton-responsiveness.
Figure 3.
Schematic illustration of molecular devices based on electron/proton-responsive Ru complexes confined to a surface.
2. Molecular design of functional Ru complexes with benzimidazole ligands
2.1 Bridging ligands that contain benzimidazole groups
Benzimidazole ligands can be synthesized by the Phillips condensation reaction between an organic carboxylic acid or nitrile and o-phenylenediamine [23]. Figure 4 shows the structures of benzimidazole ligands bridging two Ru centers that have been used by our group [17, 24, 25, 26] and others [27, 28] for the preparation of dinuclear Ru complexes. Depending on the chemical structure of the linker moiety, significant electronic coupling between the two ruthenium ions is posible. In addition, the oxidation processes of the Ru centers in aqueous solution involve PCET reactions, resulting in switching of the metal–metal interaction via the change in electron density on the conjugated linker ligand.
Figure 4.
Chemical structures of benzimidazole-containing ligands that bridge two Ru centers in bis-bidentate or bis-tridentate coordination modes.
2.2 Introducing anchor groups in benzimidazole ligands
Surface modification plays an important role in controlling the electron-transfer events and chemical reactivity in photocatalysis, as well as the charge-transport process in heterojunctions. Recently, several reviews of the applications of surface modification toward dye-sensitized solar cells and electrochemical catalysts for hydrogen/oxygen-evolution reactions have been published [21, 29, 30, 31, 32, 33, 34], showing the importance of such interdisciplinary research. In the area of solar-energy conversion, Grätzel-type dye-sensitized solar cells composed of mesoporous TiO2 on fluorine-doped SnO2 (FTO) with immobilized Ru complexes that contain 2,2′-bipyridyl-4,4′-dicarboxylate and other bpy-derived ligands have been developed [35]. Interestingly, the electron-injection efficiency from the photoexcited-state Ru complex to TiO2 was found to strongly dependent on the anchoring group [34, 36, 37].
Given that the adsorption strength of a Ru complex on a surface depends on the combination of the anchoring group and the surface material, judicious selection of both is necessary for effective surface functionalization. Recently, indium-tin oxide (ITO)-coated glass or polymer substrates have been employed in a wide variety of electronic display devices such as organic light-emitting diodes (OLEDs) [38]. Transparent ITO electrodes are also employed as cell windows for spectroelectrochemistry. Therefore, ITO is a suitable substrate for monitoring both the electrochemical and spectrochemical changes in redox-active Ru complexes immobilized on its surface. The phosphonic acid group, which is known to immobilize on ITO electrodes, has been employed to anchor the Ru complexes [39]. Furthermore, organic phosphonic acids are known to bind zirconium(IV) ions to form a solid two-dimensional layer structure, [40]. which demonstrates their suitability for use in a layer-by-layer growth method based on redox-active metal complexes. Therefore, we developed several new tridentate benzimidazole ligands with phosphonic acid or phosphonate ester anchor groups (Figure 5). Alkylation of the imino N–H groups of the benzimidazole moieties using bromoalkyl-diethylphosphonate derivatives furnished chelating benzimidazolyl ligands with ethyl-protected phosphonates, which were used for the synthesis of Ru complexes [41]. After the ethyl-protected phosphonate Ru complexes had been purified, the diethyl phosphonate groups were deprotected to provide the corresponding Ru complexes with phosphonic acid groups. In particular, the tridentate ligand XP (Figure 5) contains several methylene groups on its side-arms; these methylene moieties are sterically hindered, thus fixing the conformation of the phosphonic acid anchor groups upon surface immobilization.
Figure 5.
Chemical structures of benzimidazole-containing ligands with phosphonic acid anchor groups and their abbreviations.
2.3 Molecular design of redox-active Ru complexes with anchor groups
Ru complexes are substitutionally inert, and the octahedral coordination geometry around the Ru ion is maintained throughout the Ru(II/III) redox reaction. Therefore, they can be immobilized on a surface to design redox-active molecular devices. When three bidentate ligands are coordinated to an octahedral Ru complex, the formation of Δ and Λ optical isomers is possible, but in the case of Ru complexes surrounded by two tridentate ligands with C2v symmetry, no optical isomers do not exist. Hence, surface-confined Ru complexes that contain tridentate ligands with C2v symmetry such as 2,6-bis(benzimidazolyl)pyridine with phosphonic acid anchors are often selected for surface immobilization [21, 42]. Furthermore, the molecular orientation of Ru complexes self-assembled on a surface is crucial to the construction of further layered structures. To maintain the vertical orientation of the Ru complexes on a surface, free-standing multipodal anchor groups with phosphonic acid have been developed over the last two decades. Several examples are shown in Figure 6 [21, 43, 44, 45, 46]. together with our multipodal tridentate benzimidazole ligand with phosphonate anchors, XP.Figure 7 shows a new series of rod-shaped Ru complexes with 2,6-bis(benzimidazolyl)pyridine moieties and bi- or tetrapodal phosphonic acid groups at both ends that have been reported by our group. Mononuclear Ru complex 10 exhibits a spherical-shaped structure around the central Ru ion, while the other dinuclear Ru complexes 8, 9, 11, and 12 exhibit a rod-like structure with a Ru–Ru axis [21, 43]. When the dinuclear Ru complexes are immobilized on a surface, the Ru–Ru axis can be oriented vertically or horizontally relative to the surface plane. In AFM measurements, the obtained molecular heights of the dinuclear Ru complexes 9, 10, and 11 immobilized on an ITO surface were consistent with the predicted heights for the vertical orientation of the dinuclear Ru complexes at the ITO surface. Ru complexes 8–12 can be dissolved in aqueous solution by adjusting the solution pH, given that the phosphonic acid groups at both ends of these act as polybasic acids.
Figure 6.
Chemical structures of free-standing multipodal phosphonic acid anchor groups on a surface [43, 44, 45].
Figure 7.
Chemical structures of rod-shaped dinuclear Ru complexes that bear free-standing multipodal anchor groups at both ends.
3. Characterization and functionality of surface-immobilized redox-active Ru complexes
3.1 Surface modification by Ru complexes bearing phosphonic acid anchors
When Ru complexes bearing phosphonic acid anchors are immobilized on an ITO or mica surface by immersion of the substrate into a solution of the Ru complex, the surface coverage of the Ru complex is dependent on the immersion time and the concentration of the complex in the solution. The temporal evolution of the surface coverage can be analyzed using the kinetic Langmuir equation (Eq. (1)), and curve fitting with a rate constant parameter, k.
Γt=Γs1−exp−kC∗tE1
Here, Γ(t), k, C, and t refer to the surface coverage, rate constant, concentration of the Ru complex, and time, respectively [33, 46]. A typical kinetic plot for a Ru–XP complex with an acridine group at the top is shown in Figure 8. This surface-immobilized Ru–XP complex is able to capture double-stranded DNA from solution [46].
Figure 8.
Chemisorption kinetics of the Ru–XP complex determined by the temporal evolution of the surface coverage of the Ru–XP complex (right) on a mica surface. (left) Plot of contact angle versus immersion time [46].
Another chemical approach to evaluate the surface coverage is using the thermodynamic Langmuir isotherm based upon the concentration dependence of the adsorption of the Ru complex.
ΓiΓs−Γi=expΔGadsoRTCBE2
Here, Γi,Γs,CB,andΔGads refer to the surface adsorption at a given concentration, the adsorption at saturation, the concentration of the bulk solution, and the free energy of adsorption, respectively. The adsorption of a Ru complex on a mica and ITO surface can be fitted with the typical Langmuir isotherm model. The free energy of adsorption for Ru complex 9 was found to be −33.4 kJ/mol.
In recent years, several binding modes for the absorption of phosphonic acid groups on metal oxides have been proposed based on intensive studies using polarization modulation infrared reflection adsorption spectroscopy (PM-IRRAS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations in recent years, and the bidentate or tridentate binding modes are considered to be most probable (Figure 9) [30, 32, 34, 44, 47]. The optimum solution pH value for the adsorption of Ru complexes 8–12 depends on the complex; i.e., pH = 6 is optimal for complexes 8–11, while pH = 4 is better for complex 12.
Figure 9.
Proposed surface binding modes of phosphonic acid groups on a metal oxide (MOx) surface (M = metal) [30].
Atomic force microscopy (AFM) measurements have been used to provide clear surface images depicting the adsorption of these Ru complexes, particularly the surface morphology (e.g. height and surface coverage). Figure 10 shows AFM images of Ru complex 9 on a flattened ITO surface. The samples were prepared using two different immersion conditions, i.e., a dilute solution of the Ru complex with a short immersion time (1 μM; 10 min) and a higher concentration solution with a longer immersion time (25 μM; 3 h). As shown on the left in Figure 10, for the dilute condition, scattered dots were observed on the surface. The average height of the dots was approximately 4 μm, which is consistent with the height that was predicted for vertically oriented complex 9 using a molecular model. The AFM image on the right in Figure 10 shows that the surface was fully covered with spherical domains with a diameter of ∼20–50 μm when the concentrated conditions were used.
Figure 10.
AFM images of dinuclear Ru complex 9 immobilized on a flat ITO surface using either a 1 μM solution of complex 9 with an immersion time of 10 min (left) or a 25 mM solution for 3 h (right). Plots show cross-sectional height profiles. In the schematic drawings of the surface images, 9 is shown as a cylinders.
One advantage of ITO electrodes is that they enable the use of UV–vis spectroscopy to monitor the surface immobilization process. Ru(II) complexes bearing N-heteroaromatic ligands exhibit a relatively strong metal-to-ligand charge transfer (MLCT) band in the visible wavelength region. In particular, the temporal changes during the immobilization or multilayering processes of such complexes on modified ITO substrates are easily monitored via the absorbance changes in the UV–vis spectra. Furthermore, electrochemical methods such as cyclic voltammetry (CV) can be used to determine the surface coverage of redox-active Ru complexes immobilized on an ITO electrode [48].
3.2 PCET reaction of Ru-benzimidazole complexes in solution and on ITO electrodes
Ru complexes with benzimidazole derivative ligands act as Brønsted acids and exhibit proton-coupled electron transfer (PCET) reactions in aqueous solution [49, 50]. For example, [Ru(mbibzim)(bibzimH2)]2+ (13) (mbibzim = 2,6-bis(1-methylbenzimidazol-2-yl)pyridine and bibzimH2 = 2,6-bis(benzimidazole-2-yl)pyridine) behaves as a dibasic acid, as shown in Figure 11. The Ru(II/III) oxidation potential of 13, which results from a PCET reaction, strongly depends on the pH-value (2 < pH < 9) in a Britton–Robinson buffer/CH3CN(1:1 v/v) solution [14, 49, 50]. The PCET reaction of 13 can be described by the square scheme in Figure 12, in which complex 13 is abbreviated as Ru–LH2. This reaction involves both electron transfer and proton-transfer equilibria. In the half-wave potential/pH plot of 13, the so-called Pourbaix diagram, the half-wave potential is gradually shifted in the negative potential direction with increasing solution pH (Figure 13). Based on this diagram, the pKa values of 13 were determined to be 6.31 and 7.94 for the Ru(II) oxidation state, and < 2 and 3.60 for the Ru(III) oxidation state. When the central pyridine group in the bibzimH2 ligand is replaced with a cyclometallated phenylene group, the resulting Ru complex 14 shows a lower Ru(II/III) oxidation potential than complex 13; the pKa values of 14 also increase compared to those of 13, i.e., to 10.91 and > 12 for the Ru(II) oxidation state and to 6.46 and 9.15 for the Ru(III) oxidation state [51].
Figure 11.
Stepwise proton-transfer equilibria of Ru(II)(LMe)(LH2) complexes (13: X = N; 14: X = C) that act as Brønsted dibasic acids. The total charge of the Ru complex is omitted.
Figure 12.
Square scheme of the electron–proton equilibria of Ru complexes 13 or 14 as dibasic acids. Numbers in parentheses indicate the Ru species present in the Pourbaix diagram in Figure 13.
Figure 13.
Pourbaix diagram of Ru complex 13 in CH3CN/BR buffer (1/1 v/v) [51].
In biological systems, protons play a very important role in reactions and energy storage. Proton gradients are the driving force for the synthesis of ATP in biological membranes. Applications of proton gradients in energy storage in materials chemistry have shown that PCET chemical systems can be used for energy storage in redox batteries and capacitors. Ru complexes 13 and 14, which show PCET with different potentials and pKa values in unbuffered aqueous solutions, have been used to construct two half-cells separated by a Nafion membrane [51]. The Pourbaix diagrams of complexes 13 and 14 are shown in Figure 14; the initial oxidation states of 13 and 14 were Ru(II) and Ru(III), respectively. Upon charging, the oxidation of 13 from the Ru(II) to the Ru(III) state releases the proton(s), while the reduction of 14 from Ru(III) to Ru(II) at the other half-cell captures the proton(s). As a result, the electrical energy was stored as a pH gradient between the half-cells. The concept of using a PCET system in this way had been implemented with organic quinone derivatives, [52] but its scope was extended to redox-flow batteries by using a pH-tunable Fe(III) azamacrocyclic complex as both the catholyte and anolyte based on the multiple protonated forms of the Fe complex [53].
Figure 14.
Pourbaix diagram for a solution redox battery based on a pair of Ru complexes, 13 and 14, which both exhibit PCET reactions in CH3CN/BR buffer (1/1 v/v).
The PCET chemistry of Ru complexes that contain benzimidazole derivatives in solution can be extended to surface-bound systems by attaching surface-anchoring groups to the Ru complexes as described in the previous section.
Dinuclear Ru complexes 15, 16, and 17 (Figure 15) have N–H sites that can be deprotonated on the bridging ligand and the phosphonic acid anchoring groups at both ends. When 15 and 16 are assembled on an ITO electrode, the surface-immobilized redox-active Ru(II) complexes exhibit a well-defined CV response with a typical shape derived from adsorbed chemical species [20]. Figure 16 shows the CV responses that originate from the Ru(II/III) oxidation process of immobilized complex 15 at different pH values; these responses arise from a well-defined two-electron oxidation wave corresponding to the Ru(II)–Ru(II)/Ru(III)–Ru(III) PCET process in 15 [24]. Upon changing the pH of the aqueous solution was changed, Ru complexes 8–17 immobilize stably via the phosphonic acid groups on the ITO electrode at pH = 1.0–9.0, but at pH >9.5, the Ru complexes easily detached from the ITO surface.
Figure 15.
Chemical structures of dinuclear Ru complexes bearing both a benzimidazole bridging ligand from which protons can dissociate and free-standing multipodal phosphonic acid anchor groups at both ends [24].
Figure 16.
Cyclic voltammograms of Ru complex 15 immobilized on an ITO electrode at different pH values in CH3CN-BR buffer (1/1 v/v) [24].
The anodic peak current, ipa, is expressed as shown in Eq. (3), where n, ν, A, and Γ represent the number of electrons, scan rate, electrode area, and surface coverage, respectively. Therefore, the anodic peak current for complex 15 is linearly proportional to the scan rate ν, indicating that the Ru complex is a surface-bound species. The total area of the anodic wave is related to the surface coverage of the Ru complex, which was determined to be 0.80 × 10−10 mol cm−2.
ipa=n2F2ν4RTAΓE3
Given that the spectral change due to the redox reactions of a monolayer film of 15 on the ITO electrode can be observed by UV–vis spectroscopy, even surface-assembled monolayer films of Ru complexes on an ITO electrode can be detected. Upon the oxidation of 15 under an applied potential of +0.8 V vs. Ag–AgCl at pH = 6.5, the differential absorption spectrum demonstrates strong bleaching of the MLCT band at 550 nm and π-π* transitions of the ligands at 364 nm, along with absorbance increases at 400 and ∼ 750 nm, which are characteristic spectral features of Ru(III)–L complexes [24].
3.3 Fabrication of multilayer films based on Ru complexes by layer-by-layer (LbL) growth
Surface modification using a molecular monolayer film alone enables only a single set of functionalities to be incorporated, and the measurable physical quantities, such as optical absorption or current value, are very low due to the low molecular density on the surface. On the other hand, multi-layer modification has the advantages of allowing various molecular units to be deposited at the surface, achieving greater increases in physical quantities such as optical density and charge stored, and enables the integration of various functionalities at the interface [31]. Thus, the integration of functional metal complexes on an electrode holds great promise for applications in e.g. molecular-based devices for photochemical energy production/transduction, photocatalysis, and information storage, among other applications [54]. To achieve this integration, the LbL assembly method, in which multilayer structures are constructed via molecular interactions between two layers on a solid surface, is an appropriate technique [39]. LbL assembly using electrostatic interactions, [55]. hydrogen bonding, and coordination metal–ligand bonds has been reported [21, 56]. Among these, structures based on metal-coordination assembly are robust toward environmental changes, such as variations in pH or ionic strength, in aqueous solution.
The formation of well-ordered zirconium(IV) bisphosphonate multilayer films is a well-known method for LbL assemblies on a solid surface that has been developed by Mallouk and others [40]. This method is based on the reconstitution of a two-dimensional layered compound, Zr(HPO3)2, on a gold surface via self-assembly of molecular units with metal ions. Starting from self-assembled 4-mercaptobutylphosphonic acid on the gold surface as a primer layer, alternate immersion of the modified gold substrate into a zirconium(IV) oxychloride solution and a bisphosphonic acid solution leads to multilayer films composed of a two-dimensional zirconium–phosphonate framework structure via LbL growth [40].
Similarly, the rod-shaped Ru complexes 8–16 with polyphosphonic acid groups at both ends were immobilized by self-assembly on an ITO electrode. The polyphosphonic acids at one side of the complexes were attached to the ITO surface, while the other side of the polyphosphonic acid groups remained free to interact with metal ions in solution. Multilayer films of the Ru complexes could thus be obtained by successive alternate immersion in a zirconium(IV) ion and a Ru complex solution (Figure 17) [57]. The immobilized Ru film on the ITO substrate was monitored via UV–vis spectroscopy, CV, and the AFM-surface-scratching method throughout each stage of the LbL growth. The use of these monitoring techniques during LbL growth is shown in Figure 18 with the combination of Ru complex 11 and zirconium as an example.
Figure 17.
Illustration of the layer-by-layer (LbL) assembly by successive immersion of a solid substrate such as ITO, mica, or a Si wafer into (i) a solution of a given Ru complex with phosphonate anchors, and (ii) a solution of Zr(IV) ions. After washing, this immersion process was conducted repeated several times.
Figure 18.
Illustration of the LbL multilayer film of 11 and monitoring of its LbL growth using UV–vis spectroscopy, CV, and the AFM-scratching method, together with a plot of the height of the scratch vs. the number of layers.
In each physical measurement, the physical quantities, such as absorbance, amount of charge, and the height of the scratch increased linearly with increasing number of layers. Two types of growth models have been proposed for LbL growth from the surface-primer points via metal coordination on a solid surface (Figure 19) [59]. The first model involves dendritic divergent growth, which would result in an exponential increase in the physical quantities, while the second model involves linear growth of a layered structure. In the case of Ru complex 11, the linear increase in the physical quantities such as absorbance indicates the formation of well-ordered two-dimensional multilayer films on the solid surfaces.
Figure 19.
Illustration of two-layer-growth models: Dendritic divergent growth (left) and linear growth (right) [58].
The use of the LbL method on a solid surface makes it possible to accumulate various molecular units with different chemical functionalities by adjusting the number of layers and metals in the multilayer films. Furthermore, the sequential order of the various complex units can be varied; the units can be arranged in order of descending or ascending potential or pKa to produce hetero-multilayer films. Such gradients in the layers play an important role in energy transduction. Therefore, “coordination programming” at the surface is possible via judicious choice of molecular units [60]. For example, when two different complexes A and B are assembled into a four-layered film on a solid substrate and a primer layer A is fixed as the first immobilized layer, seven combinations can be obtained by varying the order of the successive layers (substrate|ABAB, |AAAB, etc.). As a result, various films with different potential gradients can be created, and their rectification of electron transfer can be evaluated. Finally, in the fabrication of heterolayers using metal-coordination via the LbL method by immersion in solutions of each component, it is important to ensure that each layer is segregated and that the components are not mixed with others within the layer. In particular, care should be taken using metal ions with substitutionally labile properties, such as Ni(II) and Co(II) ions.
3.4 Functionality of LbL-multilayer films based on Ru complexes
3.4.1 Electron-transfer rate in homo-multilayer Ru complex films on ITO electrodes
Measuring electron-transfer events in multilayer LbL films composed of redox-active Ru complexes on an ITO electrode is fundamental to determine whether electrons can be transmitted through the multiple layers of Ru complexes as the number of layers is increased.
CV measurements of homo-multilayer films of 11 (X = N) to evaluate their electron-transfer rate showed two one-electron oxidation waves. With increasing number of layers, the peak current during CV increased almost linearly. The peak-potential separation between the anodic and cathodic waves was unchanged at a scan rate of 0.1 V·s−1, but at 1 V·s−1, the separation increased with an increasing number of layers. Using Laviron’s procedure, [61] the heterogeneous electron-transfer rate between the Ru complexes in the layers and the ITO electrode was determined for different numbers of layers. The electron-transfer rates gradually decreased with increasing number of layers, and a small attenuation coefficient was obtained from the slope of the plots of ln(kapp) as a function of the thickness of films (L). The dependence of the electron-transfer rate, kapp, on the distance is expressed by the following equation:
kapp=k0exp−βLE4
In addition, potential-step chronoamperometry (PSCA) measurements furnished a relatively small value for the apparent electron-transfer rate, kapp (β = 0.014 Å−1) [62].
Multi-layer films of ruthenium complex 9 were grown on an ITO substrate using hydrogen-bonding interactions. In these films, free-standing ruthenium complexes of 9 adsorbed on an ITO electrode via its tetrapod phosphonic acid anchors interacts with complexes of 9 that are dissolved in the solution via multiple hydrogen bonds between the free phosphonic acid groups at its surface and those of the complex 9 in solution at pH = 6. Surprisingly, the film thickness of the resulting multiply hydrogen-bonded system was controlled by the immersion time and the solution pH. The current–voltage (I–V) characteristics of the multilayered Ru film grown on ITO were measured with a sandwich-type two-terminal devices using the conductive polymer PEDOT:PSS as the top electrode. Based on the observed current, the value of the coefficient for the attenuation with increasing film thickness was relatively small (β = 0.012–0.021Å−1) [43]. This small β value for the multilayer Ru complex film system indicates that long-range electron transport can be expected to be possible even though the system exhibits low conductivity. To clarify the reason for the long-range electron transport in the Ru multilayer film despite its low conductivity, first-principles calculations using Green’s non-equilibrium function technique and theoretical analysis of the experimental results were performed. The results indicated that the metal centers covered with the π electrons of the ligands become “stepping stone” sites that provide a resonant tunneling mechanism [43]. Small β values were also reported for terpyridine-metal-complex nanowires produced by the sequential metal-coordination method [63].
3.4.2 Redox-active LbL multilayer films in redox capacitors
As portable electronic devices continue to proliferate, cost-effective cheap energy storage devices that are small, flexible, and low cost and provide high performance during the charging and discharging cycle are in high demand. Molecular-based supercapacitors are promising candidates in terms of these requirements. Redox-active Ru complexes are suitable for the fabrication of energy storage devices, since multilayer molecular Ru assemblies obtained via the LbL method can be scaled by increasing the number of layers, which leads to enhancement of the electrical capacitance in such films [57].
The charge–discharge properties of a sixty-five-layer film of Ru complex 11, ITO|(Ru complex 11)65, were examined under galvanostatic experimental conditions by applying various constant current densities from 10 to 100 μA·cm−2. The galvanostatic charge and discharge curves show two small plateaus at 0.12 V and 0.37 V vs. Pt, which correspond to two reversible Ru(II)/Ru(III) redox processes (Figure 20). A maximum capacitance of 92.2 F·g−1 was found at an applied current density of 10 μA·cm−2, but the capacitance decreased to 63.3 F·g−1 at the highest current density of 100 μA·cm−2 (Figure 20). Stability tests of the Ru multilayer films (>1000 galvanostatic charge–discharge cycles) showed a capacitance retention of 72% [57].
Figure 20.
Galvanostatic charge–discharge curves of ITO|(Ru complex 11)65 in CH3CN/0.1 M HClO4 at different current densities [57].
3.4.3 PCET reactions in Ru-multilayer films for energy storage devices
PCET reactions can be used in energy-storage devices such as redox-flow batteries or two half-cells in unbuffered aqueous solution as described in Section 4.2. The frameworks of dinuclear Ru complexes 16 and 17 are basically formed by chemical modification of the mononuclear Ru complexes 13 and 14 via the C–C coupling of two 13 or 14 units. Thus, the PCET behaviors of complexes 16 and 17 were almost the same as those of 13 and 14, except that the number of electrons involved in the PCET reaction was doubled to result in a two-electron process due to the C–C coupling of two molecular units of 13 and 14 and the surface immobilization on an electrode. The Ru complexes 16 and 17 were immobilized by the LbL method on an ITO electrode and applied in a redox capacitor device, in which an aqueous solution was sandwiched between two electrodes composed of multilayer films of 16 and 17 to evaluate the cell performance (Figure 21) [20]. Under galvanostatic conditions at a constant current density of 10 μA·cm−2, stable charge–discharge behavior occurred, as shown in Figure 21.
Figure 21.
Schematic illustration of two half-cells composed of multilayer ITO|(16)n and ITO|(17)n (top), galvanostatic charge–discharge curves for 16 and 17 with different layer numbers, n (bottom left), and a plot of the capacitance as a function of n (bottom right) [20].
During the charging process, the multilayer 16 acted as the anode and the following oxidation reaction proceeded, resulting in the release of protons:
Ru(II)2LNH2⟶Ru(III)2LN+2e−+2H+.E5
At the same time, the multilayer electrode of 17 acted as a cathode, and the following reduction took place, resulting in the capture of protons:
Ru(III)2LCH3+2e−+H+⟶Ru(II)2LcH4.E6
where 16 and 17 are represented as Ru2LNHn and Ru2LCHn, and LNHn and LCHn indicate the bridging ligand bearing the indicated number of protons on the benzimidazole groups. In other words, the capacitance increased with an increasing number of layers [20].
On the other hand, when all four imino N–H protons on the benzimidazole moieties were protected by N–Me groups, the capacitance decreased by 77% compared to that of the original PCET-type capacitor. This result strongly suggests that the proton movement plays a more important role than the anion movement in the charge storage. Furthermore, the proton movement accompanying the redox reaction in the Ru multilayer films on the ITO electrode was confirmed using a pH-indicator probe in aqueous solution. In this type of LbL films composed of Ru complexes that exhibit PCET-type redox reactions, the capacitance increases almost linearly with the number of layers (Figure 21) [20].
To obtain proton rocking-chair-type redox capacitors that use protons as the charge carriers, the quinone/hydroquinone couple is often used [52, 64, 65, 66, 67]. However, at neutral pH, the electron–proton transfer rate of the quinone/hydroquinone couple is slower than that of the Ru(II/III) couple. The use of the LbL method to fabricate multilayered structures of redox-active Ru complexes that exhibit PCET is advantageous, as the storage capacity can be enhanced by increasing the number of redox-active modular units on demand.
3.5 Sequentially assembled heterolayer films of Ru complexes
One advantage of the LbL assembly method using metal coordination at the interface is that a combinatorial approach can be employed to construct sequentially ordered hetero-multilayer films(cf. Section 4.3).
Monolayer films of the Ru complexes 11 and 12 on ITO showed two well-defined CV waves at +0.83 and + 1.04 V and at −0.37 and + 0.09 V vs. Fc+/Fc, which were assigned to Ru(II)–Ru(II)/Ru(II)–Ru(III) and Ru(II)–Ru(III)/Ru(III)–Ru(III) processes, respectively. Due to the large differences between the potentials of 11 and 12, heterolayer films made from combinations of 11 and 12 exhibited interesting electronic/photonic behaviors such as electron-transfer blocking, rectification, and vectorial photoelectron transfer. Figure 22 shows the CV responses of the heterolayer films ITO|(11)n/(12)n (n = 1, 2, where n stands for the number of layers) and ITO|(12)n/(11)n (n = 1,3) and the alternating heterolayer films ITO|(11/12)4 and ITO|(12/11)4 in CH3CN (0.1 M HClO4) [22, 62]. The ITO|(11)1/(12)1 bilayer hetero-film exhibited four waves (Figure 22a), which correspond to the redox processes from both the inner 11 and outer 12 layers; the Ru(II)–Ru(III)/Ru(III)–Ru(III) process of 11 and the Ru(III)–Ru(III)/Ru(III)–Ru(IV) process of 12 overlap at +1.11 V. However, the peak separation of the outer layer of 12 increased at higher scan rates, while the peak separation for the waves from the inner layer of 11 remained unaffected. This result indicated a slower ET rate from the outer layer of 12 due to the higher spatial separation relative to the inner 11 film [22].
Figure 22.
Cyclic voltammograms of heterolayer films of Ru complexes 11 and 12 with varying sequences: (a) ITO|(11)n/(12)n (n = 1, 2, where n stands for the number of layers), (b) ITO|(12)n/(11)n (n = 1, 3), (c) alternating ITO|(11/12)4 and (d) ITO|(12/11)4 in CH3CN (0.1 M HClO4) [22, 62].
Conversely, for the ITO||(11)2|(12)2 hetero-film, in the first scan over the potential range of −0.5 V to +0.7 V vs. Fc+/Fc, only oxidative waves from 11 at +0.83 and + 1.04 V vs. Fc+/Fc were present; no waves from the outer 12 layer were observed (see blue line in Figure 22a). However, when the potential was scanned in the negative direction to −0.5 V, a large cathodic wave appeared at approximately −0.5 V vs. Fc+/Fc, and subsequently, a new anodic pre-peak at approximately +0.64 V (marked as x) was observed in the potential scan in the positive direction. The new pre-peak x was assigned as a catalytic oxidation wave derived from the ET of the outer 12 layers through ET mediation; that is, direct ET from the outer 12 layer to the electrode was blocked by the bilayer of 11, and an avalanche ET from the outer 12 layers to the inner holes in 11 occurred through the potential gradient once a hole was generated in the inner 11 layers at the onset of the first 11 oxidation wave (Figure 23). Consequently, the large cathodic peak at −0.5 V was assigned to the catalytic reduction wave of the 12 film mediated by the reduction process of the inner 11 film. Furthermore, the sequence of the 11 and 12 layers on the ITO electrode leads to characteristic CV responses depending on the sequence and the number of layers, as shown in Figure 22 [62].
Figure 23.
Rectified ET mechanism for the CV response of the ITO||(11)2|(12)2 hetero-film shown in Figure 22a [22].
Silicon-based pn heterojunctions play an important role in various types of electronic devices, such as diodes, transistors, solar cells and light-emitting diodes (LEDs). The potential difference at the pn junction causes blockage of charge transport, resulting in a rectification effect. Under photoirradiation, current flows through the external circuit, which acts as a silicon-based solar cell. Similarly, the photo-response of Ru-complex heterolayer films has been examined [22]. Photoirradiation of the ITO|(11)4/(12)4 hetero-multilayer film in CH3CN (0.1 M HClO4) at the open circuit potential of +0.45 V produced a cathodic photocurrent. The action spectrum of this film is nearly identical to the UV–vis absorption spectrum of 11, which indicates the inner 11 layers are the main contributor to the photoexcitation, although little photo-response was observed for homo-Ru–complex multilayer films such as ITO|(11)n or ITO|(12)n. Interestingly, the direction of the photocurrent on the ITO|(11)4/(12)4 heterolayer film switched from cathodic to anodic after the application of a potential pulse at −0.5 V. This photo-response change arose from the generation of a charge trapping state after the application of the pulse; the outer layers of 12 were reduced by the potential, and this reduced state was maintained as a charge-trapping state until holes were generated on the inner 11 layers by electrochemical oxidation or photoexcitation. This charge trapping state was recognized from the differential Vis–NIR spectra, in which a new inter-valence charge-transfer (IVCT) band at 1140 nm appeared for the mixed-valence state of 12 (Figure 24). Thus, the heterolayer film ITO|(11)4/(12)4 represents a typical example of a photo-responsive memory device; the writing process is achieved by applying a potential of either −0.5 or + 0.7 V, and the readout process is achieved by measuring the direction of the photocurrent [22]. Accordingly, the judicious selection of both redox potentials and the sequential ordering of the Ru modular units on the ITO surface makes it possible to design functional electronic devices such as molecular diodes and memory devices.
Figure 24.
Switching between the “0” and “1” states by applying potentials of −0.5 V and + 0.7 V in the ITO|(11)4/(12)4 hetero-film (top), and the corresponding photocurrent responses (bottom) [22].
4. Molecular-device applications using Ru complexes on ITO
The idea of molecular devices is based on a next-generation paradigm to overcome the limitations associated with Moore’s law, which states that the number of transistors per silicon chip doubles every year, and the use of individual molecules as active electronic components. The first single molecular device was the theoretical proposal of a molecular diode by Aviram and Ratner; [68] subsequently, the concept of molecular electronic devices was further developed by Carter [69]. Various molecules have demonstrated basic electronic functionality as switches, as diodes for rectification, and as optical devices, storage devices, and sensing devices for future information technologies [54, 70]. The recent experimental development of single-molecular conductance measurements using metal–molecule–metal junctions [71] has opened a new avenue for the realization of molecular electronic devices through the judicious selection of molecules [70, 72, 73, 74, 75, 76]. Ru complexes are substitutionally inert in both the Ru(II) and Ru(III) oxidation states, and also exhibit fast self-exchange ET rates due to the small reorganization energy of the Ru(II/III) couple. Therefore, the use of a mixed-valence Ru(II)–Ru(III) complex as a perturbing motif branching from a conducting molecular wire has been proposed by Carter. Here, two molecular devices based on Ru complexes are discussed; the first is a Ru-complex molecular junction that exhibits rectification switching in response to humidity, and the other is a two-terminal memristor device based on the PCET reactions of Ru complexes.
4.1 Rectification switching in Ru complex molecular junctions in response to external humidity
Conductive-probe atomic force microscopy (C-AFM) was employed to measure the I–V characteristics of self-assembled monolayers of Ru complexes on an ITO electrode. An ITO-coated Pt probe was used as the C-AFM tip in order to employ the same material for the top and bottom electrode, and the I–V curves were measured via the two-terminal method [77].
Under dry (low humidity) conditions, the I–V plots of both mononuclear 10 and dinuclear complex 11 became symmetric in the positive and negative potential range, indicating that the molecules at the junction behaved as a molecular wire or resistor (Figure 25). However, under the wet (high humidity) conditions, the I–V curves became asymmetric and showed diode-like behavior only for dinuclear Ru complex 11, while they remained symmetric for 10. The rectification ratio R (= |I(-V)|/|I(V)| was found to have a high value of ∼1000, where |I(V)| represents the absolute value of the forward or reverse current density at a certain voltage. When the measurement conditions were changed from wet to dry, the I–V plots for 11 became symmetric again. This rectification switching via humidity change occurred repeatedly for 11 (Figure 26); conversely, such switching was not observed for 10 [77].
Figure 25.
Structures of Ru complexes 10 (top) and 11 (bottom), log |I|–V curves of the 10 and 11 molecular junctions under low humidity (5%) and high humidity (60%) conditions, and 2D histograms of the rectification ratio (R) at high humidity [77].
Figure 26.
Conceptual illustration of a humidity-switchable molecular diode [78].
Several factors need to be considered to explain this behavior. The tip-radius affected the asymmetry of the I–V curves, whereby a small tip (50 nm radius) leading to a larger rectification ratio R on account that water molecules were more strongly attracted to the smaller tip. However, this effect could not fully explain the absence of asymmetry for 10. Based on combined theoretical and experimental results, water molecules and counter-ion displacement have an important influence on two localized molecular orbitals in 11, and under an applied voltage bias, a large asymmetry was induced externally via water molecules screening the counter-ions. Thus, via these rectifying properties, the self-assembled Ru complex 11 molecular junctions act as nanoscale sensors with ON/OFF switching in response to external humidity [77].
4.2 Protonic memristor devices based on Ru complexes with PCET
Recently, memristors have attracted substantial attention as the fourth passive element after resistors, capacitors, and inductors. The memristor was predicted by Chua in 1971 as a new electronic circuit element linking charge and magnetic flux, [79] and the first example of such a device was demonstrated experimentally in 2008. This first memristor device consisted of TiO2-x sandwiched between two Pt metal terminals, in which the oxygen defects led to filament formation, and the defects acted as mobile charged dopants and drifted in the applied electric field [80]. As a result, the device exhibited a periodic pinched hysteresis loop in its I–V curves. Since then, not only metal oxides, but also many other materials such as organic polymers and metal chalcogenide films, have been sandwiched between the two terminals to fabricate devices with a non-linear hysteretic I–V loop [81, 82]. In the two-terminal devices, non-linear changes in the current occur during the voltage sweep, and the associated resistance changes. This type of electric element is generally referred to as a memristor. In recent years, the memristor has become relevant in the context of the action of synapses in the neuromorphic systems of the brain. In biological synapses, ion/molecule migration is used for signal transduction. Inspired by the ion migration in the synapse system, we developed a system in which a proton serves as the charge carrier at the interface between Ru complexes with PCET properties and a proton-conducting polymer such as poly(4-vinylpyridine) (P4VP). In Section 4.4.3, a charge-storage system was constructed from two electrodes modified with films of the Ru complexes 16 and 17, which show PCET properties in unbuffered 0.1 M NaClO4 solution, and the resulting two-terminal cells showed a stable charging–discharging process via a proton rocking-chair-type mechanism. The unbuffered aqueous solution was replaced with proton-conducting P4VP (pKa ∼ 4.0–5.2), and the resulting two-terminal heterolayer device, ITO|(16)3/P4VP/(17)3|ITO, was tested. Figure 27 shows the typical I–V characteristics of the two-terminal device, which produced “8” shaped and non-linear I–V loop curves [83].
Figure 27.
I–V plots of the two-terminal device ITO|(16)3/P4VP/(17)3|ITO, showing ten scans on the same device. The blue line indicates the average of the ten scans [83].
To elucidate the coupling of the proton-transfer ability of P4VP and the PCET reactions of Ru complexes 16 and 17 at the hetero-interface, CV measurements were performed in 0.1 M NaClO4 aqueous solution (Figure 28). A large negative potential shift was observed for the Ru(II/III) peak of the ITO|(16)3/P4VP film compared to that of ITO|(16)3 without P4VP. This negative potential shift arises from the hydrogen-bonding interactions between the N–H benzimidazolyl groups in 16 and the pyridine groups in P4VP, based on a previous study of the hydrogen-bonding interactions between the N–H imino groups in Ru–benzimidazole-derivative complexes and N-heteroaromatics such as pyridine [84]. In this study, the magnitude of the shift was strongly correlated to the pKa values of both components (i.e., the complex and the heteroaromatic component) [84]. On the other hand, only a small potential shift was observed between the peak of the ITO|(17)3/P4VP film and that of ITO|(17)3 without P4VP. The difference between these two systems was attributed to the pKa difference between the Ru complexes in the Ru(II) and Ru(III) oxidation states.
Figure 28.
Cyclic voltammograms of ITO|(16)3/P4VP (blue solid lines) and ITO|(17)3/P4VP films (red solid lines), together with those of ITO|(16)3 (blue dotted lines) and ITO|(17)3 films (red dotted lines), in 0.1 M NaClO4 aqueous solution, as well as a schematic illustration of the hydrogen-bonding interactions between the Ru complex 16 and the P4VP polymer [83].
In the initial stage, the 16 site of the two terminal device ITO|(16)3/P4VP/(17)3|ITO is in the Ru(II) oxidation state with pKa values in the range of 4.1–8.8, while the 17 site on the other side is in the Ru(III) state with pKa values in the range of 5.2–9.8. The pKa value of the intervening P4VP polymer is 4.0–5.2. Thus, the proton gradient across the interfaces is small, and it is equilibrated through hydrogen bonding between the P4VP and both 16 and 17 (Figure 29). When a bias potential of +1.5 V is applied to the two-terminal ITO|(16)3/P4VP/(17)3|ITO device, redox processes occur on the immobilized Ru complexes, namely, the oxidation of 16 from the Ru(II) state to Ru(III) takes place at the positive-potential side of the terminal, accompanied by the reduction of 17 from the Ru(III) state to Ru(II) at the other terminal. The resulting redox reactions induce large changes in the pKa of 16 and 17 relative to those of their initial Ru(II) or Ru(III) states, resulting in a large proton gradient across the immobilized Ru complex/P4VP interfaces (Figure 11). Specifically, the pKa of 16 drops to <3.8, which means that protons are easily released upon the oxidation of 16, while on the 17 side, the pKa increases to >8.4. Given the pKa value of the intervening P4VP is 4.0–5.2, the (16)/P4VP proton transfer equilibrium is shifted toward the protonation of the P4VP side, while at the (17)/P4VP side, the equilibrium shifts toward the protonation of the film of 17 upon reduction of the Ru center. The proton conductivity through the protonated P4VP layer is improved by the resulting large pKa gradient, resulting in enhanced conduction until the opposite redox reactions take place at both terminals. When the bias potential was scanned in the negative direction toward −1.5 V, the pKa gradient returned to the initial state, and the current decreased in the absence of a driving force for electron or proton transport between 16/P4VP and P4VP/17.
Figure 29.
Schematic illustration of the proton-conduction switching in the two-terminal device ITO|(16)3/P4VP/(17)3|ITO and the pKa gradient under the applied positive bias potential. The numbers refer to the pKa values of the Ru(II) and Ru(III) complexes [83].
Therefore, the large pKa difference in the Ru complexes 16 and 17 induced by the PCET redox reactions at the two terminals cause a proton gradient across the intervening proton-conducting P4VP, leading to high proton conductivity under an applied voltage. The change in the proton gradient due to the PCET redox reaction in the two-terminal device can be applied to use the proton-conducting switching devices as protonic memristors [83].
5. Miscellaneous devices based on Ru–benzimidazole complexes for solar-energy transduction
Further important applications for ruthenium complexes include photoredox catalysts and dye-sensitized solar cells. In particular, Ru(bpy)3 or Ru(tpy)2 derivatives have been used as photosensitizer dyes on mesoporous TiO2 surfaces in Grätzel-type solar cells. Over the past two decades, many Ru complexes with phosphonate anchors have been reported, [33] and many Ru dyes derived from Ru(bpy)3 derivatives that contain phosphonate anchors (Figure 30). Additionally, Ru-2,6-bis(benzimidazole-2-yl)pyridine complexes have been employed as photoredox catalysts [85, 86]. The Ru–benzimidazole bond is known to be more stable than the Ru–pyridine bond in the photoexcited state, rendering such Ru-benzimidazole complexes promising candidates for photoelectrochemical redox catalysts.
Figure 30.
Chemical structures of Ru(bpy)3 derivatives that contain phosphonic acid anchors and surface-confined Ru catalyst and chromophore–catalyst assemblies [85, 86].
6. Conclusion
Substitutionally inert ruthenium complexes bearing benzimidazole derivatives have unique electrochemical and photochemical properties. In particular, proton-coupled electron-transfer in ruthenium–benzimidazole complexes endows them with rich redox chemistry and makes them useful as a modular unit for redox mediators or reactive sites for switching by external stimuli. In this chapter, the role of PCET reactions on Ru–benzimidazole complexes in energy-storage applications and the tuning of metal–metal interactions in aqueous solution was emphasized first. Based on this knowledge acquired from solution chemistry, the chemistry of Ru complexes confined on an electrode surface via their self-assembling from solution for the fabrication of the surface functional molecular devices on electrodes was discussed. Indium-tin oxide (ITO) is often chosen as the electrode due to its transparency and wide use as a substrate in electronics. To immobilize the redox-active Ru complexes on an ITO electrode, tetrapod phosphonic acid anchor groups are often incorporated into tridentate 2,6-bis(benzimidazole-2-yl)pyridine or benzene ligands, which enables the construction of free-standing self-assembled monolayer structures on an ITO electrode. Starting from this monolayer as a primer layer, multilayer films can be constructed by the LbL layer growth method. The resulting multilayers using redox-active Ru complexes as a modular unit exhibited long-range electron transport even in films with over 60 layers (∼100 nm thick) through the “stepping-stone” mechanism. Furthermore, a combinatorial approach to LbL layer growth can be used to obtain bespoke functional heterolayer films via material design. Using this strategy, blocking of electron transfer or rectification can be made to occur in such Ru complex heterolayer films, which results in charge trapping; the trapped electrons can subsequently be released via photo-irradiation, which leads to the new concept of photo-responsive memory devices. The CV response of multilayer films of Ru complexes with PCET depends strongly on the pH value. By judicious selection of the redox potentials and pKa values of the two Ru complexes with PCET properties, two-electrode cells based on the Ru complex multilayer films that acted as proton rocking-chair-type redox capacitors can be obtained. Furthermore, by sandwiching a proton-conducting polymer between two Ru multilayer terminals, new type of protonic memristor device can be fabricated.
Therefore, surface-confined Ru complexes exhibit highly promising potential for the development of new functional molecular-based devices.
Acknowledgments
The author gratefully acknowledges financial support from MEXT via Grants-in-Aid for Scientific Research, No. 21108003 (Coordination Programming) and JP17H05383 (Coordination Asymmetry) as well as from the Institute of Science and Engineering at Chuo University. The author would also like to thank Dr. Katsuaki Kobayashi, Prof. Katsuhiko Kanaizuka, Dr. Hiroaki Ozawa, as well as all of his past students and coauthors in my papers for their great help and their contributions.
Dedication
This chapter is dedicated to my good friend Prof. Wolfgang Kaim on the occasion of his 70th birthday, and to my late wife, Masako Haga, who has supported my research activities for many years.
\n',keywords:"Ru benzimidazole complex, surface immobilization, layer-by-layer assembly, molecular devices, redox chemistry, proton-coupled electron transfer (PCET), heterolayer, multilayer film, memory, phosphonic acid, redox capacitor, protonic memristor",chapterPDFUrl:"https://cdn.intechopen.com/pdfs/76178.pdf",chapterXML:"https://mts.intechopen.com/source/xml/76178.xml",downloadPdfUrl:"/chapter/pdf-download/76178",previewPdfUrl:"/chapter/pdf-preview/76178",totalDownloads:242,totalViews:0,totalCrossrefCites:0,dateSubmitted:null,dateReviewed:"March 6th 2021",datePrePublished:"April 8th 2021",datePublished:"January 26th 2022",dateFinished:"April 8th 2021",readingETA:"0",abstract:"Substitutionally inert ruthenium complexes bearing benzimidazole derivatives have unique electrochemical and photochemical properties. In particular, proton coupled electron transfer (PCET) in ruthenium–benzimidazole complexes leads to rich redox chemistry, which allows e.g. the tuning of redox potentials or switching by deprotonation. Using the background knowledge from acquired from their solution-state chemistry, Ru complexes immobilized on electrode surfaces have been developed and these offer new research directions toward functional molecular devices. The integration of surface-immobilized redox-active Ru complexes with multilayer assemblies via the layer-by-layer (LbL) metal coordination method on ITO electrodes provides new types of functionality. To control the molecular orientation of the complexes on the ITO surface, free-standing tetrapodal phosphonic acid anchor groups were incorporated into tridentate 2,6-bis(benzimidazole-2-yl)pyridine or benzene ligands. The use of the LbL layer growth method also enables “coordination programming” to fabricate multilayered films, as a variety of Ru complexes with different redox potentials and pKa values are available for incorporation into homo- and heterolayer films. Based on this strategy, many functional devices, such as scalable redox capacitors for energy storage, photo-responsive memory devices, proton rocking-chair-type redox capacitors, and protonic memristor devices have been successfully fabricated. Further applications of anchored Ru complexes in photoredox catalysis and dye-sensitized solar cells may be possible. Therefore, surface-confined Ru complexes exhibit great potential to contribute to the development of advanced functional molecular devices.",reviewType:"peer-reviewed",bibtexUrl:"/chapter/bibtex/76178",risUrl:"/chapter/ris/76178",signatures:"Masa-aki Haga",book:{id:"6832",type:"book",title:"Ruthenium",subtitle:"An Element Loved by Researchers",fullTitle:"Ruthenium - An Element Loved by Researchers",slug:"ruthenium-an-element-loved-by-researchers",publishedDate:"January 26th 2022",bookSignature:"Hitoshi Ishida",coverURL:"https://cdn.intechopen.com/books/images_new/6832.jpg",licenceType:"CC BY 3.0",editedByType:"Edited by",isbn:"978-1-83962-917-4",printIsbn:"978-1-83962-916-7",pdfIsbn:"978-1-83962-922-8",isAvailableForWebshopOrdering:!0,editors:[{id:"210140",title:"Dr.",name:"Hitoshi",middleName:null,surname:"Ishida",slug:"hitoshi-ishida",fullName:"Hitoshi Ishida"}],productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"}},authors:[{id:"327682",title:"Prof.",name:"Masa-Aki",middleName:null,surname:"Haga",fullName:"Masa-Aki Haga",slug:"masa-aki-haga",email:"mhaga83@gmail.com",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/327682/images/15483_n.jpg",institution:{name:"Chuo University",institutionURL:null,country:{name:"Japan"}}}],sections:[{id:"sec_1",title:"1. Introduction",level:"1"},{id:"sec_2",title:"2. Molecular design of functional Ru complexes with benzimidazole ligands",level:"1"},{id:"sec_2_2",title:"2.1 Bridging ligands that contain benzimidazole groups",level:"2"},{id:"sec_3_2",title:"2.2 Introducing anchor groups in benzimidazole ligands",level:"2"},{id:"sec_4_2",title:"2.3 Molecular design of redox-active Ru complexes with anchor groups",level:"2"},{id:"sec_6",title:"3. Characterization and functionality of surface-immobilized redox-active Ru complexes",level:"1"},{id:"sec_6_2",title:"3.1 Surface modification by Ru complexes bearing phosphonic acid anchors",level:"2"},{id:"sec_7_2",title:"3.2 PCET reaction of Ru-benzimidazole complexes in solution and on ITO electrodes",level:"2"},{id:"sec_8_2",title:"3.3 Fabrication of multilayer films based on Ru complexes by layer-by-layer (LbL) growth",level:"2"},{id:"sec_9_2",title:"3.4 Functionality of LbL-multilayer films based on Ru complexes",level:"2"},{id:"sec_9_3",title:"3.4.1 Electron-transfer rate in homo-multilayer Ru complex films on ITO electrodes",level:"3"},{id:"sec_10_3",title:"3.4.2 Redox-active LbL multilayer films in redox capacitors",level:"3"},{id:"sec_11_3",title:"3.4.3 PCET reactions in Ru-multilayer films for energy storage devices",level:"3"},{id:"sec_13_2",title:"3.5 Sequentially assembled heterolayer films of Ru complexes",level:"2"},{id:"sec_15",title:"4. Molecular-device applications using Ru complexes on ITO",level:"1"},{id:"sec_15_2",title:"4.1 Rectification switching in Ru complex molecular junctions in response to external humidity",level:"2"},{id:"sec_16_2",title:"4.2 Protonic memristor devices based on Ru complexes with PCET",level:"2"},{id:"sec_18",title:"5. Miscellaneous devices based on Ru–benzimidazole complexes for solar-energy transduction",level:"1"},{id:"sec_19",title:"6. Conclusion",level:"1"},{id:"sec_20",title:"Acknowledgments",level:"1"},{id:"sec_20",title:"Dedication",level:"1"}],chapterReferences:[{id:"B1",body:'Higgins S. Regarding ruthenium. Nat Chem. 2010;2:1100-1100.'},{id:"B2",body:'Seddon EA, Seddon KR. The Chemistry of Ruthenium. Amsterdam, The Netherlands: Elsevier; 1984.'},{id:"B3",body:'Holder AA, Lilge L, Browne WR, Lawrence MAW, Bullock JL, editors. Ruthenium Complexes: Photochemical and Biomedical Applications. 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Computational design of molecules for an all-quinone redox flow battery. Chem Sci. 2015;6(2):885-893. DOI: 10.1039/c4sc03030c.'},{id:"B65",body:'Tomai T, Mitani S, Komatsu D, Kawaguchi Y, Honma I. Metal-free aqueous redox capacitor via proton rocking-chair system in an organic-based couple. Sci Rep. 2014;4:3591. DOI: 10.1038/srep03591.'},{id:"B66",body:'Ji Y, Goulet MA, Pollack DA, Kwabi DG, Jin S, Porcellinis D, et al. A phosphonate-functionalized quinone redox flow battery at near-neutral pH with record capacity retention rate. Adv. Energy Mater. 2019;9(12) DOI: 10.1002/aenm.201900039.'},{id:"B67",body:'Wedege K, Draževič E, Konya D, Bentien A. Organic redox species in aqueous flow batteries: Redox potentials, chemical stability and solubility. Sci Rep. 2016;6:39101. DOI: 10.1038/srep39101.'},{id:"B68",body:'Aviram A, Ratner MA. Molecular rectifiers. Chem Phys Lett. 1974;29:277 - 283.'},{id:"B69",body:'Carter FL. The molecular device computer:point of departure for larger scale cellular automata. Physica D. 1984;10:175-194.'},{id:"B70",body:'Jeong H, Kim D, Xiang D, Lee T. High-yield functional molecular electronic devices. ACS Nano. 2017;11(7):6511-6548. DOI: 10.1021/acsnano.7b02967.'},{id:"B71",body:'Xu B, Tao NJ. Measurement of single-molecule resistance by repeated formation of molecular junctions. Science. 2003;301:1221-1223.'},{id:"B72",body:'Schwarz F, Kastlunger G, Lissel F, Riel H, Venkatesan K, Berke H, et al. High-conductive organometallic molecular wires with delocalized electron systems strongly coupled to metal electrodes. Nano Lett. 2014;14(10):5932-5940. DOI: 10.1021/nl5029045.'},{id:"B73",body:'Aradhya SV, Venkataraman L. Single-molecule junctions beyond electronic transport. Nat Nanotechnol. 2013;8(6):399-410 DOI: 10.1038/nnano.2013.91.'},{id:"B74",body:'Meng F, Hervault Y-M, Shao Q, Hu B, Norel L, Rigaut S, et al. Orthogonally modulated molecular transport junctions for resettable electronic logic gates. Nat. Commun. 2014;5:3023.'},{id:"B75",body:'Milan DC, Vezzoli A, Planje IJ, Low PJ. Metal bis(acetylide) complex molecular wires: concepts and design strategies. Dalton Trans. 2018;47:14125 - 14138.'},{id:"B76",body:'Tanaka Y, Kato Y, Tada T, Fujii S, Kiguchi M, Akita M. “Doping” of polyyne with an organometallic fragment leads to highly conductive metallapolyyne molecular wire. J Amer Chem Soc. 2018;140:10080 - 10084.'},{id:"B77",body:'Atesci H, Kaliginedi V, Celis Gil JA, Ozawa H, Thijssen JM, Broekmann P, et al. Humidity-controlled rectification switching in ruthenium-complex molecular junctions. Nat Nanotechnol. 2018;13(2):117-121. DOI: 10.1038/s41565-017-0016-8.'},{id:"B78",body:'https://mom.dcb.unibe.ch/mom_pages/mom_2018-02.html.'},{id:"B79",body:'Chua L. Memristor-The missing circuit element. IEEE Trans Circuit Theory. 1971;18:507-519.'},{id:"B80",body:'Strukov DB, Snider GS, Stewart DR, Williams RS. The missing memristor found. Nature 2008;453(7191):80-83. DOI: 10.1038/nature06932.'},{id:"B81",body:'Bessonov AA, Kirikova MN, Petukhov DI, Allen M, Ryhanen T, Bailey MJA. Layered memristive and memcapacitive switches for printable electronics. Nat Mater. 2015;14(2):199-204. DOI: 10.1038/nmat4135.'},{id:"B82",body:'Chua L. Five non-volatile memristor enigmas solved. Appl. Phys. A. 2018;124(8):563. DOI: 10.1007/s00339-018-1971-0.'},{id:"B83",body:'Hiruma Y, Yoshikawa K, Haga M. Bio-inspired protonic memristor devices based on metal complexes with proton-coupled electron transfer. Faraday Discuss. 2019;213:99-113. DOI: 10.1039/c8fd00098k.'},{id:"B84",body:'Haga M, Tsunemitsu A. The outer-sphere interactions in ruthenium and osmium complexes I. Spectrophotometric and voltammetric studies on the hydrogen bonding interactions of bis(2,2’-bipyridine)(2-(2’-pyridyl)benzimidazole)ruthenium(II) cation and its derivatives with aromatic nitrogen heterocycles. Inorg Chim Acta. 1989;164:137-142.'},{id:"B85",body:'Tamaki Y, Ishitani O. Supramolecular photocatalysts constructed with a photosensitizer unit with two tridentate ligands for CO2 reduction. Faraday Discuss. 2017;198:319-335. DOI: 10.1039/c6fd00220j.'},{id:"B86",body:'Ashford DL, Gish MK, Vannucci AK, Brennaman MK, Templeton JL, Papanikolas JM, et al. Molecular chromophore–catalyst assemblies for solar fuel applications. Chem Rev. 2015;115(23):13006-13049. DOI: 10.1021/acs.chemrev.5b00229.'}],footnotes:[],contributors:[{corresp:"yes",contributorFullName:"Masa-aki Haga",address:"mhaga@kc.chuo-u.ac.jp",affiliation:'
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She received her PhD in Sustainable Architecture from the University of Huddersfield-UK, where she got The Vice Chancellor’s Award for an Outstanding Research Degree Thesis. Dr. Salman has gained her professional experience through studying and working in a number of institutions in UK, Canada, and The Middle East. Maha has worked at the University of Toronto teaching “Contemporary Architecture” and “Postcolonial Studies in Architecture” in addition to supervising a number of independent studies. Since 2009, Dr. Salman has joined Yorkville University where she taught several theory and studio based courses including: Research Methodologies, Philosophy of Design, Sustainability & Materials, Global Architecture and Design, Canadian Architecture, Documentation, and Moving Spaces. 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\r\n\tScientists have long researched to understand the environment and man’s place in it. The search for this knowledge grows in importance as rapid increases in population and economic development intensify humans’ stresses on ecosystems. Fortunately, rapid increases in multiple scientific areas are advancing our understanding of environmental sciences. Breakthroughs in computing, molecular biology, ecology, and sustainability science are enhancing our ability to utilize environmental sciences to address real-world problems. \r\n\tThe four topics of this book series - Pollution; Environmental Resilience and Management; Ecosystems and Biodiversity; and Water Science - will address important areas of advancement in the environmental sciences. They will represent an excellent initial grouping of published works on these critical topics.
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He is also a faculty member in the Molecular Oncology Program. He obtained his MSc and Ph.D. at Oregon State University and Texas Tech University, respectively. He pursued his postdoctoral studies at Rutgers University Medical School and the National Institutes of Health (NIH/NIDDK), USA. His research focuses on biochemistry, biophysics, genetics, molecular biology, and molecular medicine with specialization in the fields of drug design, protein structure-function, protein folding, prions, microRNA, pseudogenes, molecular cancer, epigenetics, metabolites, proteomics, genomics, protein expression, and characterization by spectroscopic and calorimetric methods.",institutionString:"University of Health Sciences",institution:null},{id:"180528",title:"Dr.",name:"Hiroyuki",middleName:null,surname:"Kagechika",slug:"hiroyuki-kagechika",fullName:"Hiroyuki Kagechika",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/180528/images/system/180528.jpg",biography:"Hiroyuki Kagechika received his bachelor’s degree and Ph.D. in Pharmaceutical Sciences from the University of Tokyo, Japan, where he served as an associate professor until 2004. He is currently a professor at the Institute of Biomaterials and Bioengineering (IBB), Tokyo Medical and Dental University (TMDU). From 2010 to 2012, he was the dean of the Graduate School of Biomedical Science. Since 2012, he has served as the vice dean of the Graduate School of Medical and Dental Sciences. He has been the director of the IBB since 2020. Dr. Kagechika’s major research interests are the medicinal chemistry of retinoids, vitamins D/K, and nuclear receptors. He has developed various compounds including a drug for acute promyelocytic leukemia.",institutionString:"Tokyo Medical and Dental University",institution:{name:"Tokyo Medical and Dental University",country:{name:"Japan"}}},{id:"94311",title:"Prof.",name:"Martins",middleName:"Ochubiojo",surname:"Ochubiojo Emeje",slug:"martins-ochubiojo-emeje",fullName:"Martins Ochubiojo Emeje",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/94311/images/system/94311.jpeg",biography:"Martins Emeje obtained a BPharm with distinction from Ahmadu Bello University, Nigeria, and an MPharm and Ph.D. from the University of Nigeria (UNN), where he received the best Ph.D. award and was enlisted as UNN’s “Face of Research.” He established the first nanomedicine center in Nigeria and was the pioneer head of the intellectual property and technology transfer as well as the technology innovation and support center. 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In 2001, he went to the University of Tennessee Health Science Center (UTHSC) in USA, where he was a post-doctoral researcher and focused on mass spectrometry and cancer proteomics. Then, he was appointed as an Assistant Professor of Neurology, UTHSC in 2005. He moved to the Cleveland Clinic in USA as a Project Scientist/Staff in 2006 where he focused on the studies of eye disease proteomics and biomarkers. He returned to UTHSC as an Assistant Professor of Neurology in the end of 2007, engaging in proteomics and biomarker studies of lung diseases and brain tumors, and initiating the studies of predictive, preventive, and personalized medicine (PPPM) in cancer. In 2010, he was promoted to Associate Professor of Neurology, UTHSC. Currently, he is a Professor at Xiangya Hospital of Central South University in China, Fellow of Royal Society of Medicine (FRSM), the European EPMA National Representative in China, Regular Member of American Association for the Advancement of Science (AAAS), European Cooperation of Science and Technology (e-COST) grant evaluator, Associate Editors of BMC Genomics, BMC Medical Genomics, EPMA Journal, and Frontiers in Endocrinology, Executive Editor-in-Chief of Med One. He has\npublished 116 peer-reviewed research articles, 16 book chapters, 2 books, and 2 US patents. His current main research interest focuses on the studies of cancer proteomics and biomarkers, and the use of modern omics techniques and systems biology for PPPM in cancer, and on the development and use of 2DE-LC/MS for the large-scale study of human proteoforms.",institutionString:null,institution:{name:"Xiangya Hospital Central South University",country:{name:"China"}}},{id:"40482",title:null,name:"Rizwan",middleName:null,surname:"Ahmad",slug:"rizwan-ahmad",fullName:"Rizwan Ahmad",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/40482/images/system/40482.jpeg",biography:"Dr. Rizwan Ahmad is a University Professor and Coordinator, Quality and Development, College of Medicine, Imam Abdulrahman bin Faisal University, Saudi Arabia. Previously, he was Associate Professor of Human Function, Oman Medical College, Oman, and SBS University, Dehradun. Dr. Ahmad completed his education at Aligarh Muslim University, Aligarh. He has published several articles in peer-reviewed journals, chapters, and edited books. His area of specialization is free radical biochemistry and autoimmune diseases.",institutionString:"Imam Abdulrahman Bin Faisal University",institution:{name:"Imam Abdulrahman Bin Faisal University",country:{name:"Saudi Arabia"}}},{id:"41865",title:"Prof.",name:"Farid A.",middleName:null,surname:"Badria",slug:"farid-a.-badria",fullName:"Farid A. Badria",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/41865/images/system/41865.jpg",biography:"Farid A. Badria, Ph.D., is the recipient of several awards, including The World Academy of Sciences (TWAS) Prize for Public Understanding of Science; the World Intellectual Property Organization (WIPO) Gold Medal for best invention; Outstanding Arab Scholar, Kuwait; and the Khwarizmi International Award, Iran. He has 250 publications, 12 books, 20 patents, and several marketed pharmaceutical products to his credit. 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He has more than sixteen years of teaching experience and has supervised numerous postgraduate and Ph.D. students. He has to his credit more than seventy papers in SCI- and SCOPUS-indexed journals, fifty-five conference proceedings, four books, six Best Paper Awards, and five projects from different government agencies. He is currently an editorial board member of eight international journals and a reviewer for more than fifty scientific journals. He received Top Reviewer and Excellent Peer Reviewer Awards from Publons in 2016 and 2017, respectively. He is also on the panel of The International Reviewer for reviewing research proposals for grants from the Royal Society. He also serves as a Publons Academy mentor and Bentham brand ambassador.",institutionString:"Punjab Technical University",institution:{name:"Punjab Technical University",country:{name:"India"}}},{id:"142388",title:"Dr.",name:"Thiago",middleName:"Gomes",surname:"Gomes Heck",slug:"thiago-gomes-heck",fullName:"Thiago Gomes Heck",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/142388/images/7259_n.jpg",biography:null,institutionString:null,institution:{name:"Universidade Regional do Noroeste do Estado do Rio Grande do Sul",country:{name:"Brazil"}}},{id:"336273",title:"Assistant Prof.",name:"Janja",middleName:null,surname:"Zupan",slug:"janja-zupan",fullName:"Janja Zupan",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/336273/images/14853_n.jpeg",biography:"Janja Zupan graduated in 2005 at the Department of Clinical Biochemistry (superviser prof. dr. Janja Marc) in the field of genetics of osteoporosis. Since November 2009 she is working as a Teaching Assistant at the Faculty of Pharmacy, Department of Clinical Biochemistry. In 2011 she completed part of her research and PhD work at Institute of Genetics and Molecular Medicine, University of Edinburgh. She finished her PhD entitled The influence of the proinflammatory cytokines on the RANK/RANKL/OPG in bone tissue of osteoporotic and osteoarthritic patients in 2012. From 2014-2016 she worked at the Institute of Biomedical Sciences, University of Aberdeen as a postdoctoral research fellow on UK Arthritis research project where she gained knowledge in mesenchymal stem cells and regenerative medicine. She returned back to University of Ljubljana, Faculty of Pharmacy in 2016. She is currently leading project entitled Mesenchymal stem cells-the keepers of tissue endogenous regenerative capacity facing up to aging of the musculoskeletal system funded by Slovenian Research Agency.",institutionString:null,institution:{name:"University of Ljubljana",country:{name:"Slovenia"}}},{id:"357453",title:"Dr.",name:"Radheshyam",middleName:null,surname:"Maurya",slug:"radheshyam-maurya",fullName:"Radheshyam Maurya",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/357453/images/16535_n.jpg",biography:null,institutionString:null,institution:{name:"University of Hyderabad",country:{name:"India"}}},{id:"418340",title:"Dr.",name:"Jyotirmoi",middleName:null,surname:"Aich",slug:"jyotirmoi-aich",fullName:"Jyotirmoi Aich",position:null,profilePictureURL:"https://s3.us-east-1.amazonaws.com/intech-files/0033Y000038Ugi5QAC/Profile_Picture_2022-04-15T07:48:28.png",biography:"Biotechnologist with 15 years of research including 6 years of teaching experience. Demonstrated record of scientific achievements through consistent publication record (H index = 13, with 874 citations) in high impact journals such as Nature Communications, Oncotarget, Annals of Oncology, PNAS, and AJRCCM, etc. Strong research professional with a post-doctorate from ACTREC where I gained experimental oncology experience in clinical settings and a doctorate from IGIB where I gained expertise in asthma pathophysiology. A well-trained biotechnologist with diverse experience on the bench across different research themes ranging from asthma to cancer and other infectious diseases. An individual with a strong commitment and innovative mindset. Have the ability to work on diverse projects such as regenerative and molecular medicine with an overall mindset of improving healthcare.",institutionString:"DY Patil Deemed to Be University",institution:null},{id:"349288",title:"Prof.",name:"Soumya",middleName:null,surname:"Basu",slug:"soumya-basu",fullName:"Soumya Basu",position:null,profilePictureURL:"https://s3.us-east-1.amazonaws.com/intech-files/0033Y000035QxIDQA0/Profile_Picture_2022-04-15T07:47:01.jpg",biography:"Soumya Basu, Ph.D., is currently working as an Associate Professor at Dr. D. Y. Patil Biotechnology and Bioinformatics Institute, Dr. D. Y. Patil Vidyapeeth, Pune, Maharashtra, India. With 16+ years of trans-disciplinary research experience in Drug Design, development, and pre-clinical validation; 20+ research article publications in journals of repute, 9+ years of teaching experience, trained with cross-disciplinary education, Dr. Basu is a life-long learner and always thrives for new challenges.\r\nHer research area is the design and synthesis of small molecule partial agonists of PPAR-γ in lung cancer. She is also using artificial intelligence and deep learning methods to understand the exosomal miRNA’s role in cancer metastasis. Dr. Basu is the recipient of many awards including the Early Career Research Award from the Department of Science and Technology, Govt. of India. She is a reviewer of many journals like Molecular Biology Reports, Frontiers in Oncology, RSC Advances, PLOS ONE, Journal of Biomolecular Structure & Dynamics, Journal of Molecular Graphics and Modelling, etc. She has edited and authored/co-authored 21 journal papers, 3 book chapters, and 15 abstracts. She is a Board of Studies member at her university. She is a life member of 'The Cytometry Society”-in India and 'All India Cell Biology Society”- in India.",institutionString:"Dr. D.Y. Patil Vidyapeeth, Pune",institution:{name:"Dr. D.Y. Patil Vidyapeeth, Pune",country:{name:"India"}}},{id:"354817",title:"Dr.",name:"Anubhab",middleName:null,surname:"Mukherjee",slug:"anubhab-mukherjee",fullName:"Anubhab Mukherjee",position:null,profilePictureURL:"https://intech-files.s3.amazonaws.com/0033Y0000365PbRQAU/ProfilePicture%202022-04-15%2005%3A11%3A18.480",biography:"A former member of Laboratory of Nanomedicine, Brigham and Women’s Hospital, Harvard University, Boston, USA, Dr. Anubhab Mukherjee is an ardent votary of science who strives to make an impact in the lives of those afflicted with cancer and other chronic/acute ailments. He completed his Ph.D. from CSIR-Indian Institute of Chemical Technology, Hyderabad, India, having been skilled with RNAi, liposomal drug delivery, preclinical cell and animal studies. He pursued post-doctoral research at College of Pharmacy, Health Science Center, Texas A & M University and was involved in another postdoctoral research at Department of Translational Neurosciences and Neurotherapeutics, John Wayne Cancer Institute, Santa Monica, California. In 2015, he worked in Harvard-MIT Health Sciences & Technology as a visiting scientist. He has substantial experience in nanotechnology-based formulation development and successfully served various Indian organizations to develop pharmaceuticals and nutraceutical products. He is an inventor in many US patents and an author in many peer-reviewed articles, book chapters and books published in various media of international repute. Dr. Mukherjee is currently serving as Principal Scientist, R&D at Esperer Onco Nutrition (EON) Pvt. Ltd. and heads the Hyderabad R&D center of the organization.",institutionString:"Esperer Onco Nutrition Pvt Ltd.",institution:null},{id:"319365",title:"Assistant Prof.",name:"Manash K.",middleName:null,surname:"Paul",slug:"manash-k.-paul",fullName:"Manash K. Paul",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/319365/images/system/319365.png",biography:"Manash K. Paul is a Principal Investigator and Scientist at the University of California Los Angeles. He has contributed significantly to the fields of stem cell biology, regenerative medicine, and lung cancer. His research focuses on various signaling processes involved in maintaining stem cell homeostasis during the injury-repair process, deciphering lung stem cell niche, pulmonary disease modeling, immuno-oncology, and drug discovery. He is currently investigating the role of extracellular vesicles in premalignant lung cell migration and detecting the metastatic phenotype of lung cancer via machine-learning-based analyses of exosomal signatures. Dr. Paul has published in more than fifty peer-reviewed international journals and is highly cited. He is the recipient of many awards, including the UCLA Vice Chancellor’s award, a senior member of the Institute of Electrical and Electronics Engineers (IEEE), and an editorial board member for several international journals.",institutionString:"University of California Los Angeles",institution:{name:"University of California Los Angeles",country:{name:"United States of America"}}},{id:"311457",title:"Dr.",name:"Júlia",middleName:null,surname:"Scherer Santos",slug:"julia-scherer-santos",fullName:"Júlia Scherer Santos",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/311457/images/system/311457.jpg",biography:"Dr. Júlia Scherer Santos works in the areas of cosmetology, nanotechnology, pharmaceutical technology, beauty, and aesthetics. Dr. Santos also has experience as a professor of graduate courses. Graduated in Pharmacy, specialization in Cosmetology and Cosmeceuticals applied to aesthetics, specialization in Aesthetic and Cosmetic Health, and a doctorate in Pharmaceutical Nanotechnology. Teaching experience in Pharmacy and Aesthetics and Cosmetics courses. She works mainly on the following subjects: nanotechnology, cosmetology, pharmaceutical technology, aesthetics.",institutionString:"Universidade Federal de Juiz de Fora",institution:{name:"Universidade Federal de Juiz de Fora",country:{name:"Brazil"}}},{id:"219081",title:"Dr.",name:"Abdulsamed",middleName:null,surname:"Kükürt",slug:"abdulsamed-kukurt",fullName:"Abdulsamed Kükürt",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/219081/images/system/219081.png",biography:"Dr. Kükürt graduated from Uludağ University in Turkey. He started his academic career as a Research Assistant in the Department of Biochemistry at Kafkas University. In 2019, he completed his Ph.D. program in the Department of Biochemistry at the Institute of Health Sciences. He is currently working at the Department of Biochemistry, Kafkas University. He has 27 published research articles in academic journals, 11 book chapters, and 37 papers. He took part in 10 academic projects. He served as a reviewer for many articles. He still serves as a member of the review board in many academic journals. He is currently working on the protective activity of phenolic compounds in disorders associated with oxidative stress and inflammation.",institutionString:null,institution:{name:"Kafkas University",country:{name:"Turkey"}}},{id:"178366",title:"Dr.",name:"Volkan",middleName:null,surname:"Gelen",slug:"volkan-gelen",fullName:"Volkan Gelen",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/178366/images/system/178366.jpg",biography:"Volkan Gelen is a Physiology specialist who received his veterinary degree from Kafkas University in 2011. Between 2011-2015, he worked as an assistant at Atatürk University, Faculty of Veterinary Medicine, Department of Physiology. In 2016, he joined Kafkas University, Faculty of Veterinary Medicine, Department of Physiology as an assistant professor. Dr. Gelen has been engaged in various academic activities at Kafkas University since 2016. There he completed 5 projects and has 3 ongoing projects. He has 60 articles published in scientific journals and 20 poster presentations in scientific congresses. His research interests include physiology, endocrine system, cancer, diabetes, cardiovascular system diseases, and isolated organ bath system studies.",institutionString:"Kafkas University",institution:{name:"Kafkas University",country:{name:"Turkey"}}},{id:"418963",title:"Dr.",name:"Augustine Ododo",middleName:"Augustine",surname:"Osagie",slug:"augustine-ododo-osagie",fullName:"Augustine Ododo Osagie",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/418963/images/16900_n.jpg",biography:"Born into the family of Osagie, a prince of the Benin Kingdom. I am currently an academic in the Department of Medical Biochemistry, University of Benin. Part of the duties are to teach undergraduate students and conduct academic research.",institutionString:null,institution:{name:"University of Benin",country:{name:"Nigeria"}}},{id:"192992",title:"Prof.",name:"Shagufta",middleName:null,surname:"Perveen",slug:"shagufta-perveen",fullName:"Shagufta Perveen",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/192992/images/system/192992.png",biography:"Prof. Shagufta Perveen is a Distinguish Professor in the Department of Pharmacognosy, College of Pharmacy, King Saud University, Riyadh, Saudi Arabia. Dr. Perveen has acted as the principal investigator of major research projects funded by the research unit of King Saud University. She has more than ninety original research papers in peer-reviewed journals of international repute to her credit. She is a fellow member of the Royal Society of Chemistry UK and the American Chemical Society of the United States.",institutionString:"King Saud University",institution:{name:"King Saud University",country:{name:"Saudi Arabia"}}},{id:"49848",title:"Dr.",name:"Wen-Long",middleName:null,surname:"Hu",slug:"wen-long-hu",fullName:"Wen-Long Hu",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/49848/images/system/49848.jpg",biography:"Wen-Long Hu is Chief of the Division of Acupuncture, Department of Chinese Medicine at Kaohsiung Chang Gung Memorial Hospital, as well as an adjunct associate professor at Fooyin University and Kaohsiung Medical University. Wen-Long is President of Taiwan Traditional Chinese Medicine Medical Association. He has 28 years of experience in clinical practice in laser acupuncture therapy and 34 years in acupuncture. He is an invited speaker for lectures and workshops in laser acupuncture at many symposiums held by medical associations. He owns the patent for herbal preparation and producing, and for the supercritical fluid-treated needle. Dr. Hu has published three books, 12 book chapters, and more than 30 papers in reputed journals, besides serving as an editorial board member of repute.",institutionString:"Kaohsiung Chang Gung Memorial Hospital",institution:{name:"Kaohsiung Chang Gung Memorial Hospital",country:{name:"Taiwan"}}},{id:"298472",title:"Prof.",name:"Andrey V.",middleName:null,surname:"Grechko",slug:"andrey-v.-grechko",fullName:"Andrey V. Grechko",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/298472/images/system/298472.png",biography:"Andrey Vyacheslavovich Grechko, Ph.D., Professor, is a Corresponding Member of the Russian Academy of Sciences. He graduated from the Semashko Moscow Medical Institute (Semashko National Research Institute of Public Health) with a degree in Medicine (1998), the Clinical Department of Dermatovenerology (2000), and received a second higher education in Psychology (2009). Professor A.V. Grechko held the position of Сhief Physician of the Central Clinical Hospital in Moscow. He worked as a professor at the faculty and was engaged in scientific research at the Medical University. Starting in 2013, he has been the initiator of the creation of the Federal Scientific and Clinical Center for Intensive Care and Rehabilitology, Moscow, Russian Federation, where he also serves as Director since 2015. He has many years of experience in research and teaching in various fields of medicine, is an author/co-author of more than 200 scientific publications, 13 patents, 15 medical books/chapters, including Chapter in Book «Metabolomics», IntechOpen, 2020 «Metabolomic Discovery of Microbiota Dysfunction as the Cause of Pathology».",institutionString:"Federal Research and Clinical Center of Intensive Care Medicine and Rehabilitology",institution:null},{id:"199461",title:"Prof.",name:"Natalia V.",middleName:null,surname:"Beloborodova",slug:"natalia-v.-beloborodova",fullName:"Natalia V. Beloborodova",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/199461/images/system/199461.jpg",biography:'Natalia Vladimirovna Beloborodova was educated at the Pirogov Russian National Research Medical University, with a degree in pediatrics in 1980, a Ph.D. in 1987, and a specialization in Clinical Microbiology from First Moscow State Medical University in 2004. She has been a Professor since 1996. Currently, she is the Head of the Laboratory of Metabolism, a division of the Federal Research and Clinical Center of Intensive Care Medicine and Rehabilitology, Moscow, Russian Federation. N.V. Beloborodova has many years of clinical experience in the field of intensive care and surgery. She studies infectious complications and sepsis. She initiated a series of interdisciplinary clinical and experimental studies based on the concept of integrating human metabolism and its microbiota. Her scientific achievements are widely known: she is the recipient of the Marie E. Coates Award \\"Best lecturer-scientist\\" Gustafsson Fund, Karolinska Institutes, Stockholm, Sweden, and the International Sepsis Forum Award, Pasteur Institute, Paris, France (2014), etc. Professor N.V. Beloborodova wrote 210 papers, five books, 10 chapters and has edited four books.',institutionString:"Federal Research and Clinical Center of Intensive Care Medicine and Rehabilitology",institution:null},{id:"354260",title:"Ph.D.",name:"Tércio Elyan",middleName:"Azevedo",surname:"Azevedo Martins",slug:"tercio-elyan-azevedo-martins",fullName:"Tércio Elyan Azevedo Martins",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/354260/images/16241_n.jpg",biography:"Graduated in Pharmacy from the Federal University of Ceará with the modality in Industrial Pharmacy, Specialist in Production and Control of Medicines from the University of São Paulo (USP), Master in Pharmaceuticals and Medicines from the University of São Paulo (USP) and Doctor of Science in the program of Pharmaceuticals and Medicines by the University of São Paulo. Professor at Universidade Paulista (UNIP) in the areas of chemistry, cosmetology and trichology. Assistant Coordinator of the Higher Course in Aesthetic and Cosmetic Technology at Universidade Paulista Campus Chácara Santo Antônio. Experience in the Pharmacy area, with emphasis on Pharmacotechnics, Pharmaceutical Technology, Research and Development of Cosmetics, acting mainly on topics such as cosmetology, antioxidant activity, aesthetics, photoprotection, cyclodextrin and thermal analysis.",institutionString:null,institution:{name:"University of Sao Paulo",country:{name:"Brazil"}}},{id:"334285",title:"Ph.D. Student",name:"Sameer",middleName:"Kumar",surname:"Jagirdar",slug:"sameer-jagirdar",fullName:"Sameer Jagirdar",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/334285/images/14691_n.jpg",biography:"I\\'m a graduate student at the center for biosystems science and engineering at the Indian Institute of Science, Bangalore, India. I am interested in studying host-pathogen interactions at the biomaterial interface.",institutionString:null,institution:{name:"Indian Institute of Science Bangalore",country:{name:"India"}}},{id:"329248",title:"Dr.",name:"Md. Faheem",middleName:null,surname:"Haider",slug:"md.-faheem-haider",fullName:"Md. Faheem Haider",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/329248/images/system/329248.jpg",biography:"Dr. Md. Faheem Haider completed his BPharm in 2012 at Integral University, Lucknow, India. In 2014, he completed his MPharm with specialization in Pharmaceutics at Babasaheb Bhimrao Ambedkar University, Lucknow, India. He received his Ph.D. degree from Jamia Hamdard University, New Delhi, India, in 2018. He was selected for the GPAT six times and his best All India Rank was 34. Currently, he is an assistant professor at Integral University. Previously he was an assistant professor at IIMT University, Meerut, India. He has experience teaching DPharm, Pharm.D, BPharm, and MPharm students. He has more than five publications in reputed journals to his credit. Dr. Faheem’s research area is the development and characterization of nanoformulation for the delivery of drugs to various organs.",institutionString:"Integral University",institution:{name:"Integral University",country:{name:"India"}}},{id:"329795",title:"Dr.",name:"Mohd Aftab",middleName:"Aftab",surname:"Siddiqui",slug:"mohd-aftab-siddiqui",fullName:"Mohd Aftab Siddiqui",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/329795/images/system/329795.png",biography:"Dr. Mohd Aftab Siddiqui is an assistant professor in the Faculty of Pharmacy, Integral University, Lucknow, India, where he obtained a Ph.D. in Pharmacology in 2020. He also obtained a BPharm and MPharm from the same university in 2013 and 2015, respectively. His area of research is the pharmacological screening of herbal drugs/natural products in liver cancer and cardiac diseases. He is a member of many professional bodies and has guided many MPharm and PharmD research projects. Dr. Siddiqui has many national and international publications and one German patent to his credit.",institutionString:"Integral University",institution:null},{id:"255360",title:"Dr.",name:"Usama",middleName:null,surname:"Ahmad",slug:"usama-ahmad",fullName:"Usama Ahmad",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/255360/images/system/255360.png",biography:"Dr. Usama Ahmad holds a specialization in Pharmaceutics from Amity University, Lucknow, India. He received his Ph.D. from Integral University, Lucknow, India, with his work titled ‘Development and evaluation of silymarin nanoformulation for hepatic carcinoma’. Currently, he is an Assistant Professor of Pharmaceutics, at the Faculty of Pharmacy, Integral University. He has been teaching PharmD, BPharm, and MPharm students and conducting research in the novel drug delivery domain. From 2013 to 2014 he worked on a research project funded by SERB-DST, Government of India. He has a rich publication record with more than twenty-four original journal articles, two edited books, four book chapters, and several scientific articles to his credit. He is a member of the American Association for Cancer Research, the International Association for the Study of Lung Cancer, and the British Society for Nanomedicine. Dr. Ahmad’s research focus is on the development of nanoformulations to facilitate the delivery of drugs.",institutionString:"Integral University",institution:{name:"Integral University",country:{name:"India"}}},{id:"333824",title:"Dr.",name:"Ahmad Farouk",middleName:null,surname:"Musa",slug:"ahmad-farouk-musa",fullName:"Ahmad Farouk Musa",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/333824/images/22684_n.jpg",biography:"Dato’ Dr Ahmad Farouk Musa\nMD, MMED (Surgery) (Mal), Fellowship in Cardiothoracic Surgery (Monash Health, Aust), Graduate Certificate in Higher Education (Aust), Academy of Medicine (Mal)\n\n\n\nDato’ Dr Ahmad Farouk Musa obtained his Doctor of Medicine from USM in 1992. He then obtained his Master of Medicine in Surgery from the same university in the year 2000 before subspecialising in Cardiothoracic Surgery at Institut Jantung Negara (IJN), Kuala Lumpur from 2002 until 2005. He then completed his Fellowship in Cardiothoracic Surgery at Monash Health, Melbourne, Australia in 2008. He has served in the Malaysian army as a Medical Officer with the rank of Captain upon completing his Internship before joining USM as a trainee lecturer. He is now serving as an academic and researcher at Monash University Malaysia. He is a life-member of the Malaysian Association of Thoracic & Cardiovascular Surgery (MATCVS) and a committee member of the MATCVS Database. He is also a life-member of the College of Surgeons, Academy of Medicine of Malaysia; a life-member of Malaysian Medical Association (MMA), and a life-member of Islamic Medical Association of Malaysia (IMAM). Recently he was appointed as an Interim Chairperson of Examination & Assessment Subcommittee of the UiTM-IJN Cardiothoracic Surgery Postgraduate Program. As an academic, he has published numerous research papers and book chapters. He has also been appointed to review many scientific manuscripts by established journals such as the British Medical Journal (BMJ). He has presented his research works at numerous local and international conferences such as the European Association for Cardiothoracic Surgery (EACTS) and the European Society of Cardiovascular Surgery (ESCVS), to name a few. He has also won many awards for his research presentations at meetings and conferences like the prestigious International Invention, Innovation & Technology Exhibition (ITEX); Design, Research and Innovation Exhibition, the National Conference on Medical Sciences and the Annual Scientific Meetings of the Malaysian Association for Thoracic and Cardiovascular Surgery. He was awarded the Darjah Setia Pangkuan Negeri (DSPN) by the Governor of Penang in July, 2015.",institutionString:null,institution:{name:"Monash University Malaysia",country:{name:"Malaysia"}}},{id:"30568",title:"Prof.",name:"Madhu",middleName:null,surname:"Khullar",slug:"madhu-khullar",fullName:"Madhu Khullar",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/30568/images/system/30568.jpg",biography:"Dr. Madhu Khullar is a Professor of Experimental Medicine and Biotechnology at the Post Graduate Institute of Medical Education and Research, Chandigarh, India. She completed her Post Doctorate in hypertension research at the Henry Ford Hospital, Detroit, USA in 1985. She is an editor and reviewer of several international journals, and a fellow and member of several cardiovascular research societies. Dr. Khullar has a keen research interest in genetics of hypertension, and is currently studying pharmacogenetics of hypertension.",institutionString:"Post Graduate Institute of Medical Education and Research",institution:{name:"Post Graduate Institute of Medical Education and Research",country:{name:"India"}}},{id:"223233",title:"Prof.",name:"Xianquan",middleName:null,surname:"Zhan",slug:"xianquan-zhan",fullName:"Xianquan Zhan",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/223233/images/system/223233.png",biography:"Xianquan Zhan received his MD and Ph.D. in Preventive Medicine at West China University of Medical Sciences. He received his post-doctoral training in oncology and cancer proteomics at the Central South University, China, and the University of Tennessee Health Science Center (UTHSC), USA. He worked at UTHSC and the Cleveland Clinic in 2001–2012 and achieved the rank of associate professor at UTHSC. Currently, he is a full professor at Central South University and Shandong First Medical University, and an advisor to MS/PhD students and postdoctoral fellows. He is also a fellow of the Royal Society of Medicine and European Association for Predictive Preventive Personalized Medicine (EPMA), a national representative of EPMA, and a member of the American Society of Clinical Oncology (ASCO) and the American Association for the Advancement of Sciences (AAAS). He is also the editor in chief of International Journal of Chronic Diseases & Therapy, an associate editor of EPMA Journal, Frontiers in Endocrinology, and BMC Medical Genomics, and a guest editor of Mass Spectrometry Reviews, Frontiers in Endocrinology, EPMA Journal, and Oxidative Medicine and Cellular Longevity. He has published more than 148 articles, 28 book chapters, 6 books, and 2 US patents in the field of clinical proteomics and biomarkers.",institutionString:"Shandong First Medical University",institution:{name:"Affiliated Hospital of Shandong Academy of Medical Sciences",country:{name:"China"}}}]}},subseries:{item:{id:"25",type:"subseries",title:"Evolutionary Computation",keywords:"Genetic Algorithms, Genetic Programming, Evolutionary Programming, Evolution Strategies, Hybrid Algorithms, Bioinspired Metaheuristics, Ant Colony Optimization, Evolutionary Learning, Hyperparameter Optimization",scope:"Evolutionary computing is a paradigm that has grown dramatically in recent years. This group of bio-inspired metaheuristics solves multiple optimization problems by applying the metaphor of natural selection. It so far has solved problems such as resource allocation, routing, schedule planning, and engineering design. Moreover, in the field of machine learning, evolutionary computation has carved out a significant niche both in the generation of learning models and in the automatic design and optimization of hyperparameters in deep learning models. This collection aims to include quality volumes on various topics related to evolutionary algorithms and, alternatively, other metaheuristics of interest inspired by nature. For example, some of the issues of interest could be the following: Advances in evolutionary computation (Genetic algorithms, Genetic programming, Bio-inspired metaheuristics, Hybrid metaheuristics, Parallel ECs); Applications of evolutionary algorithms (Machine learning and Data Mining with EAs, Search-Based Software Engineering, Scheduling, and Planning Applications, Smart Transport Applications, Applications to Games, Image Analysis, Signal Processing and Pattern Recognition, Applications to Sustainability).",coverUrl:"https://cdn.intechopen.com/series_topics/covers/25.jpg",hasOnlineFirst:!1,hasPublishedBooks:!0,annualVolume:11421,editor:{id:"136112",title:"Dr.",name:"Sebastian",middleName:null,surname:"Ventura Soto",slug:"sebastian-ventura-soto",fullName:"Sebastian Ventura Soto",profilePictureURL:"https://mts.intechopen.com/storage/users/136112/images/system/136112.png",biography:"Sebastian Ventura is a Spanish researcher, a full professor with the Department of Computer Science and Numerical Analysis, University of Córdoba. Dr Ventura also holds the positions of Affiliated Professor at Virginia Commonwealth University (Richmond, USA) and Distinguished Adjunct Professor at King Abdulaziz University (Jeddah, Saudi Arabia). Additionally, he is deputy director of the Andalusian Research Institute in Data Science and Computational Intelligence (DaSCI) and heads the Knowledge Discovery and Intelligent Systems Research Laboratory. He has published more than ten books and over 300 articles in journals and scientific conferences. Currently, his work has received over 18,000 citations according to Google Scholar, including more than 2200 citations in 2020. In the last five years, he has published more than 60 papers in international journals indexed in the JCR (around 70% of them belonging to first quartile journals) and he has edited some Springer books “Supervised Descriptive Pattern Mining” (2018), “Multiple Instance Learning - Foundations and Algorithms” (2016), and “Pattern Mining with Evolutionary Algorithms” (2016). He has also been involved in more than 20 research projects supported by the Spanish and Andalusian governments and the European Union. He currently belongs to the editorial board of PeerJ Computer Science, Information Fusion and Engineering Applications of Artificial Intelligence journals, being also associate editor of Applied Computational Intelligence and Soft Computing and IEEE Transactions on Cybernetics. Finally, he is editor-in-chief of Progress in Artificial Intelligence. He is a Senior Member of the IEEE Computer, the IEEE Computational Intelligence, and the IEEE Systems, Man, and Cybernetics Societies, and the Association of Computing Machinery (ACM). Finally, his main research interests include data science, computational intelligence, and their applications.",institutionString:null,institution:{name:"University of Córdoba",institutionURL:null,country:{name:"Spain"}}},editorTwo:null,editorThree:null,series:{id:"14",title:"Artificial Intelligence",doi:"10.5772/intechopen.79920",issn:"2633-1403"},editorialBoard:[{id:"111683",title:"Prof.",name:"Elmer P.",middleName:"P.",surname:"Dadios",slug:"elmer-p.-dadios",fullName:"Elmer P. 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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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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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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. 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