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List of contributors XI
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Mahdie Matin
Endocrinology and Metabolism Research Center Endocrinology and Metabolism Clinical Sciences Institute Tehran University of Medical Sciences Tehran Iran
Mahtab Mirhoseinian
Endocrinology and Metabolism Research Center Endocrinology and Metabolism Clinical Sciences Institute Tehran University of Medical Sciences Tehran Iran
Alireza Alikhanian
Endocrinology and Metabolism Research Center Endocrinology and Metabolism Clinical Sciences Institute Tehran University of Medical Sciences Tehran Iran
Golnar Bayatani
Endocrinology and Metabolism Research Center Endocrinology and Metabolism Clinical Sciences Institute Tehran University of Medical Sciences Tehran Iran
Burak Tüzün
Plant and Animal Production Department Technical Sciences Vocational School of Sivas Sivas Cumhuriyet University Sivas Turkey
Parham Taslimi
Department of Biotechnology Faculty of Science Bartin University 74100 Bartin Turkey
Saima Ashraf
Institute of Chemical Sciences Bahauddin Zakariya University Multan 60800 Pakistan
Fahmida Jabeen
Institute of Chemical Sciences Bahauddin Zakariya University Multan 60800 Pakistan
Sabeen Iqbal
Institute of Chemical Sciences Bahauddin Zakariya University Multan 60800 Pakistan
Mohammad Nazari Montazer
Endocrinology and Metabolism Research Center Endocrinology and Metabolism Clinical Sciences Institute Tehran University of Medical Sciences Tehran Iran
Mohammad Mahdavi
Endocrinology and Metabolism Research Center Endocrinology and Metabolism Clinical Sciences Institute Tehran University of Medical Sciences Tehran Iran
Muhammad Salman Sajid
Institute of Chemical Sciences Bahauddin Zakariya University Multan 60800 Pakistan
Muhammad Naeem Ashiq
Institute of Chemical Sciences Bahauddin Zakariya University Multan 60800 Pakistan
Muhammad Najam-ul-Haq
Institute of Chemical Sciences Bahauddin Zakariya University Multan 60800 Pakistan
XII List of contributors
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Shokoh Parhama
School of Advanced Medical Technology Isfahan University of Medical Sciences Isfahan Iran; And Centre for Sustainable Nanomaterials IbnuSina Institute for Scientific and Industrial Research Universiti Teknologi Malaysia 81310 UTM Skudai, Johor Malaysia
Seyed Shirin Parham
Department of Veterinary ShahreKord Branch Islamic Azad University ShahreKord Iran
HadiNur
Centre for Sustainable Nanomaterials IbnuSina Institute for Scientific and Industrial Research Universiti Teknologi Malaysia 81310 UTM Skudai, Johor Malaysia And Central Laboratory of Minerals and Advanced Materials Faculty of Mathematics and Natural Science Universitas Negeri Malang Malang Indonesia
Anelisiwe Mbengashe
DSI/Mintek NIC Biolabels Node Department of Biotechnology University of the Western Cape Bellville South Africa
Zimkhitha Bianca Nqakala
Organometallics and Nanomaterials Department of Chemical Sciences University of the Western Cape Bellville South Africa
Antoinette Alliya Ajmal
DSI/Mintek NIC Biolabels Node Department of Biotechnology University of the Western Cape Bellville South Africa
Tswellang Mgijima
Organometallics and Nanomaterials Department of Chemical Sciences University of the Western Cape Bellville South Africa
Cate Malope Mashilo
DSI/Mintek NIC Biolabels Node Department of Biotechnology University of the Western Cape Bellville South Africa
Nicole RemaliahSamantha Sibuyi
Department of Science and Innovation (DSI)// Mintek Nanotechnology Innovation Centre (NIC) Advanced Materials Division Health Platform Mintek, Randburg, South Africa And, DSI/Mintek NIC Biolabels Node Department of Biotechnology University of the Western Cape Bellville South Africa
Aluwani Matshaya
DSI/Mintek NIC Biolabels Node Department of Biotechnology University of the Western Cape Bellville South Africa
Samantha Meyer
Department of Biomedical Sciences Faculty of Health and Wellness Sciences Cape Peninsula University of Technology Bellville South Africa
List of contributors XIII
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Mervin Meyer
DSI/Mintek NIC Biolabels Node Department of Biotechnology University of the Western Cape Bellville South Africa
Martin OpiyoOnani
Organometallics and Nanomaterials Department of Chemical Sciences University of the Western Cape Bellville South Africa
Abram MadimabeMadiehe
DSI/Mintek NIC Biolabels Node Department of Biotechnology University of the Western Cape Bellville South Africa
Adewale Oluwaseun Fadaka
DSI/Mintek NIC Biolabels Node Department of Biotechnology University of the Western Cape Bellville South Africa And Department of Anesthesia Division of Pain Management Cincinnati Children’s Hospital Medical Center Cincinnati, Ohio 45229, USA And Southern Illinois University School of Medicine 801 N. Rutledge Springfield IL 62702, USA
N.B. Iroha
Department of Chemistry Federal University Otuoke Bayelsa State Nigeria
C.O. Ezenwaka
Department of Biology Federal University Otuoke Bayelsa State Nigeria
C.N. Opara
Department of Microbiology Federal University Otuoke Bayelsa State Nigeria
F.E. Abeng
Department of Chemistry Cross River University of Technology Calabar Nigeria
Elyor Berdimurodov✶, Khasan Berdimuradov, Kholmurodov Bahodir,
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Abduvali Kholikov, Khamdam Akbarov, Omar Dagdag, Mohamed Rbaa, Brahim El Ibrahimi, Dakeshwar Kumar Verma, Rajesh Haldhar and Pramod Kumar Mahish
Chapter 1 Recent trends and developments in carbon dots
Abstract: The carbon dots are new materials in modern chemistry. The modern devel-
opment ways for carbon dots were discussed in this chapter. Currently, the carbon dots are synthesized by the top-down and bottom-up methods. The electrochemical methods, ultrasonic treatment, laser ablation method, and arc discharge method were mostly used in the top-down methods. The bottom-up methods have some advantages such as convenient methodology, precise control, easy instrumentation, cost-effectiveness, in­volvement of non-toxic precursor molecules, practical applicability, and green materials. The carbon dots are synthesized from green sources such as carbohydrates, biomass, and bio-waste. The carbon dots are modified with the supramolecular hosts to obtain theuniquecarbondotsinthebiometricelements, catalysts, and sensor applications. The carbon dots are modified to follow the 2D materials to enhance their unique properties.
Keywords: Carbon dots, top-down syntheses, bottom-up syntheses, green materials, biomass
✶
Corresponding author: Elyor Berdimurodov, Faculty of Chemistry, National University of Uzbekistan, Tashkent 100034, Uzbekistan Khasan Berdimuradov, Kholmurodov Bahodir, Faculty of Industrial Viticulture and Food Production Technology, Shahrisabz Branch of Tashkent Institute of Chemical Technology, Shahrisabz 181306, Uzbekistan Abduvali Kholikov, Khamdam Akbarov, Faculty of Chemistry, National University of Uzbekistan, Tashkent 100034, Uzbekistan Omar Dagdag, Centre for Materials Science, College of Science, Engineering and Technology, University of South Africa, Johannesburg 1710, South Africa Mohamed Rbaa, Laboratory of Organic Chemistry, Catalysis and Environment, Faculty of Sciences, Ibn Tofail University, PO Box 133, 14000 Kenitra, Morocco Brahim El Ibrahimi, Department of Applied Chemistry, Faculty of Applied Sciences, Ibn Zohr University, Agadir 86153, Morocco Dakeshwar Kumar Verma, Department of Chemistry, Government Digvijay Autonomous Postgraduate College, Rajnandgaon, Chhattisgarh 491441, India Rajesh Haldhar, School of Chemical Engineering, Yeungnam University, Gyeongsan 712749, South Korea Pramod Kumar Mahish, Department of Biotechnology, Government Digvijay Autonomous Postgraduate College, Rajnandgaon, Chhattisgarh 491441, India
https://doi.org/10.1515/9783110799958-001
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1.1 Introduction
1.1.1 Importance of carbon dots in material and engineering science
The size of carbon dots is lower than 10 nm. Carbon dots contained mainly sp2­hybridized graphitic carbon. Their important properties depend on the structural, optical, physical, chemical, and electronic performances. These materials ar e ease of functionalization, good chemical inertness, therm al stability, high water s olubility, unique luminescence properties, and low toxicity [1, 2]. Their unique performance significantly depends on the synthesis sources, which may be organic, polymer, green source, and inorganic sources. S ome obtained results confirmed that the sur­face structure, functional groups, heteroatoms, doping agents, and size are also rea­sons for their unique properties [3, 4].
Carbon dot-based nanomaterials are the new trend in material and engineering sci­ence. They are 0D materials as a new trend in drug delivery, sensing, catalysis, and bio­imaging. They have good performances such as their low-cost synthesis methodology, high biocompatibility, low toxicity, and good optical properties. These properties make them become more effective materials in modern science. The carbon dots were synthe­sized by the cost-effective and easy-operation methods [2, 5, 6]. Additionally, the sonoly­sis of carbon precursors, thermolysis, electrochemical and chemical oxidations, and laser ablation methods were also used in the carbon dot synthesis. Currently, the mostly synthesized carbon dots have the following unique properties such as exceptional
Catalytic
properties
Optical
properties
Low
toxicity
Ultra
compact
size
Figure 1.1: Unique properties of modern carbon dots [7].
Chemical
inertness
CARBON
DOTS
Minimal
photo
bleaching
Ease of
functionali
zation.
Biocompatibility
Chemical
stability
Photolumine
scence
Chapter 1 Recent trends and developments in carbon dots 3
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productivity, superior photostability, high quantum yield, biocompatibility, electrical properties, and excellent optical performances (Figures 1.1 and 1.2) [7, 8].
Figure 1.2: Main characteristics of carbon dots [9].
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1.2 Current trends in the synthesis of carbon dots
At present, the carbon dots are synthesized by the top-down and bottom-up methods. These synthesis methodologies differ from each other related to the synthesis routine, sol­vents, precursors, temperature effects, nature of components, carbon sources, and others. Solvothermal or hydrothermal methods are mostly used in current times [10, 11]. In this synthesis methodology, the small molecules (anilines, carbohydrates, amino acids, and cit­ric acid) are reacted in the auto-clap condition with high temperatures (150–270 °C) and long times in the solvent. This method is low cost and does not require any advanced equipment. The hydrothermal reactions occur in these conditions [12–14]. The micro­waveswerealsousedtoenhancethecarbondots.Thevarioustypesofprecursorsand unique performances were developed by using microwaves in the solvothermal reactions of carbon dots. The high reaction production, low amount of solvent, and low reaction time were achieved in the microwave-hydrothermal synthesis of carbon dots [15–17].
Figure 1.3: Hydrothermal preparations of carbon dots: limitations, controllable parameters, and examples [15].
On the other hand, various reactions occur at high temperatures (over 170 °C) in hydro­thermal reactors; as a result, many types of reaction products are formed. Currently, the carbon dots are cleaned from the reaction products by dialysis, heat-drying, freeze-drying, and organic extraction methods. After the cleaning process, the reaction productivity maybe reduced (Figure 1.3). These limitations would be solved by the new syntheses methodologies such as machine learning, laser synthesis in the liquid phase, flow chemistry, and mechanochemistry. These ways make the synthesis of carbon dots become more controllable, more productive, and take unique properties [15, 18–20].
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1.3 Developments in the synthesis of carbon dots
In modern times, various new strategies in the synthesis of carbon dots are being de­veloped. The main factor of carbon dots is a surface character, which is controlled by various modern methods. The studies confirmed that the functional groups are at­tached to the surface of carbon dots. For example, the hydroxyl, carboxyl, carbonyl, ether, epoxy, and amine functional groups are mainly l inked to carbon dot surface. Various heteroatoms such as boron, sulphur, phosphorous, oxygen, and nitrogen are doped on the surface by using organic, polymeric, and biological materials [21, 22].
The rise of quantum yield is an important factor in the development of the syn­thesis strategy of carbon dots. The obtained results confirmed that biological ways are more efficient techniques for the rise in quantum yield. The photoluminescence inten­sity and higher biocompatibility of carbon dots were increased with the biological synthesis ways. The biological synthesis ways required biological sources such as grass, tea leaves, coconut shell, soya beans, coffee beans, garlic, rice bran, egg, sugar beet molasses, leaves, pomegranate, banana, honey, and yoghurt [23, 24].
The top-down and bottom-up modern syntheses methods are mostly used in the development of carbon dots. The macroscopic carbonaceous materials such as graph­ite, carbon nanotubes, and activated carbon were employed in the top-down methods. Figure 1.4 shows the trends of developments of carbon dot syntheses. The electro­chemical methods, ultrasonic treatment, laser ablation method, and arc discharge method were mostly used in the top-down methods. These methods used the following conditions: high energy, high potential, laser emission, and high acidity [25, 26].
The bottom-up methods have some advantages such as convenient methodology, precise control, easy instrumentation, cost-effectiveness, involvement o f non-toxic precursor molecules, practical applicability, and green materials. However, the quan­tum yield is little. The reaction processes in this method required more time and high energies [27, 28].
1.4 Trends in green carbon dots
Green materials have an important role in modern chemistry. The carbon dots are syn­thesized from green sources such as carbohydrates, biomass, and bio-waste. The synthe­sis of carbon dots from environmentally friendly materials cannot require expensive methods and hazardous chemicals. All syntheses methodologies are green. These prop­erties promote the future materials of carbon dots [7]. The precursors were prepared from natural and synthetic compounds. The modern methods named top-down and bot­tom-up preparations have less economic and environmental impacts. In these method­ologies, high energy, expensive precursors, hazardous organic molecules, and large
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(a)
Figure 1.4: Developments in the synthesis of carbon dots: (a) strategies [29] and (b) advantages of modern methods [15].
(b)
Chapter 1 Recent trends and developments in carbon dots 7
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amounts of toxic solvents were used. Therefore, green sources of carbon dots are re­quired in modern chemistry [30–33].
The waste of biomass is a serious problem in modern times because the production of horticultural products were accumulated in the large amount. The recycling of waste biomass is very important in the modern era. The waste biomass is of low cost and is the raw material for the source of carbon dots. Many research works suggested that the carbon dots were effectively synthesized from the waste biomass [14, 34, 35]. For exam­ple, the low-size carbon dots were prepared from the coconut shell biomass. The ob­tained carbon dots are good blue-emitting carbon quantum dots and water-soluble highly fluorescent material. The carbon dots from the agricultural waste were used as an effective agent in cancer treatment. The various sources of biomass were used for carbon dot syntheses: silkworm cocoon, spent coffee grounds, pseudo-stem of banana plant, cat feedstock waste, tender coconut waste, durian peel, rice husk, waste tea resi­due, papaya waste, apple seeds, and so on. Pyrolysis, solvent-free carbonization, hydro­thermal carbonization, thermal carbonization, oxidative pyrolysis, chemical oxidation, roasting, charring, sand bath-assisted method, ultrasonic wet method, and calcination method were mostly used to synthesize carbon dots from the biomass [7]. For example, Zhao et al. synthesized carbon dots from chitosan, cellulose, lignin, and hemicelluloses by hydrothermal methods at various temperatures (150–200 °C). The synthesis proce­dure and its main properties were shown in Figure 1.5. It is indicated that the obtained carbon dots have the following good properties: environmental friendliness, excellent biocompatibility, emission wavelength, tunable excitation, and high photostability. The fluorescence performance of the obtained carbon dots was employed in the detection of copper(II) ions at low concentrations. It is confirmed that these carbon dots are more effective agents in the analytical chemistry for metal detection [36].
1.5 Carbon dot modification with supramolecular
compounds
Thecarbondotsaremodifiedwithsupramolecularhoststoobtainuniquecarbondots in the biometric elements, catalysts, and sensor applications. The host–guest interactions can promote the fluorescence performance of carbon dots (Figure 1.6). As a result, the modification of carbon dots with the supramolecular host–guest part is an effective agent in detection of biomolecules, organic compounds, anions, and metal cations. In the last 10 years, the following supramolecular host is attached to the carbon dots: the car­boxyl esterase, calixarene, resorcinarene macrocycles, crown ethers, pillar[n]arenes, and cucurbit[n]urils. These hosts interacted with the carbon dots through the covalent and non-covalent bonds. The modification of carbon dots with the above host by the hydrothermal–carbonation methods. The structural and intrinsic properties of carbon dots are improved by the supramolecular hosts. These properties are mainly responsible
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