ENGINEERING ATOMIC-SCALE CATALYTIC INTERFACES FOR BIOMOLECULE DETECTION

다국어 초록 (Multilingual Abstract)

Atomic scale catalytic material is efficient probe in biosensing applications to detect neurotransmitters. Electrochemical sensing techniques in the unique tool to develop a biosensor. Here this thesis mainly focuses on the following chapters. Chapter 1 gives the basic introduction of the nanomaterials types, and sensor application with electrochemistry, Fluorescent and energy. Chapter 2 explains the synthesized fluorescent copper cluster through the conjugation of BSA. CuNCs used to detect MPXV using electrochemical and fluorescence techniques. For point-of- care testing, a smartphone-based sensor array was used. In chapter 3 copper based SACs were synthesized by the support of BNNT for the detection of DA. Electrochemical sensing techniques were used to detect the DA. The real human serum was used to perform the sensor for real time application. Chapter 4 discussed about a composite structure as CuSACs@MxMIL, for the electrochemical sensing of NE. The synthesized CuSACs@MxMIL was then integrated onto a carbon paper electrode (CPE) to evaluate its electrochemical behavior and activity toward NE detection. In chapter 5, the successful stabilization of copper single-atom active sites on a MWCNT/FeMOF hybrid (CuSACs@MC/FM) via a simple pyrolysis approach, and we evaluated their OER, HER, and ORR performances. Chapter 6 provides overall insights of SACs towards the biosensing and energy applications. CHAPTER 1 Introduction 1.1 Introduction Nanomaterial is a specific type of material which is around 1-100 nm in size and exhibits numerous advantages in the chemical, biological and physical properties due to surface effect, size effect, and quantum size effect [1,2]. Those properties are rectifying the complications of noise, cost, sensitivity, selectivity and detection time in conventional biosensor [3]. Nanomaterials can be developed using metals, semiconductors, ceramics, polymers, and carbon-based materials. They possess large surface areas, strong quantum effects, optical characteristics that depend on their size, and unique mechanical and thermal behaviors. Nanomaterials possess a large surface area which boosts the material reaction, sensing capacity, catalytic activity, and energy conversion [4]. New and various sizes and shaped nanomaterials can be used in everyday applications like electronics, medicine, energy and environmental applications. Nanomaterials are categorized as 0D (Single Atom-Catalysts, Clusters and Nanoparticles), 1D (nano tubes and nanorods), 2D (MXene and Graphene), and 3D (MOF, nanocrystals, nanoprism and nanoflowers). Figure 1-1. Schematic diagram of different dimensional of nanomaterials The bulk materials can become nanomaterials, nanoparticles, nanoclusters and SACs. The down the size of activity materials from nanoclusters to single atoms is promising materials to provide optimal active sites leads to increase the metal atom efficiency and keep the catalytic activity in high rate. Based on the chemical interaction with mononuclear metal atom and supports like metal oxides, metal surface, MOF, Zeolites and 2D based materials. SACs are a formidable and efficient technique like individual atom coordinating or dispersed with the appropriate atom in supporting material which involves cost reduction and better catalytic activity and selectivity in sensor [5]. Figure 1-2. Schematic diagram of SACs formation

목차 (Table of Contents)

• CHAPTER 1 Introduction 1
• 1.1 Introduction 2
• 1.2 Focus on Current Research 7
• 1.2. References 10
• CHAPTER 2 Red fluorescent copper nanocluster for fluorescence, smartphone and electrochemical sensor array to detect the monkeypox A29 protein 11
• 2.1. Introduction 12
• 2.2. Materials and methods 16
• 2.2.1. Chemicals 16
• 2.2.2. Instrumentation 16
• 2.2.3. Synthesis of CuNCs 19
• 2.2.4. Fluorescence detection of A29P using CuNCs 19
• 2.2.5. Calorimetric sensor reader system for detection of A29P 20
• 2.2.6. Fabrication of Ab A29 immunoprobe for electrochemical detection 22
• 2.2.7. Immunodetection of A29P protein 22
• 2.3. Results and discussion 23
• 2.3.1. Morphological and Analytical Studies 23
• 2.3.2. XPS study before and after sensing of the A29P using CuNCs 26
• 2.3.3. Fluorescence sensing of A29P 31
• 2.3.4. Smartphone detection of A29P 34
• 2.3.5. Electrochemical detection of A29P 34
• 2.3.6. Optimization of experimental conditions 40
• 2.3.7. Chronoamperometric studies 41
• 2.3.8. Reproducibility and Interference Study 44
• 2.3.9. Plausible mechanisms 45
• 2.4. Conclusion 46
• 2.5. References 48
• CHAPTER 3 Cu single-atom catalysts on BNNTs for sensitive electrochemical detection of Dopamine in human serum 55
• 3.1. Introduction 56
• 3.2. Materials and methods 60
• 3.2.1. Synthesis of CuSACs@BNNT 60
• 3.2.2. Characterization 62
• 3.2.3. Surface modification of GCE 62
• 3.2.4. Electrochemical detection of CuSACs@BNNT with modified GCE 63
• 3.3. Results and discussions 64
• 3.3.1. Synthesis and Morphological characterization of Cu@BNNT 64
• 3.3.2. XPS spectroscopic analysis 67
• 3.3.3. Electrochemical analysis of CuSACs@BNNT 67
• 3.3.4. Electrochemical analysis of CuSACs@BNNT towards DA 69
• 3.4. Conclusion 75
• 3.5. References 76
• CHAPTER 4 Cu single-atom catalysts on MxMIL framework for electrochemical sensing of norepinephrine 83
• 4.1. Introduction 84
• 4.2. Experimental section 87
• 4.2.1. Materials 87
• 4.2.2. Synthesis methods 87
• 4.2.3. Characterization techniques 90
• 4.2.4. Electrochemical working electrode preparation 91
• 4.2.5. Electrochemical characterization and measurements 92
• 4.3. Results and discussion 93
• 4.3.1. Morphological characterization 93
• 4.3.2. Analytical characterization 94
• 4.3.3 Electrochemical behavior of CuSACs@MxMIL 101
• 4.3.4. Electrochemical behavior of CuSACs@MxMIL towards NE 105
• 4.4 Conclusion 109
• 4.5. References 110
• CHAPTER 5 Copper-single atom architecture on MWCNT/Fe- MOF heterostructure for efficient H2 and H2O2 in alkaline media 113
• 5.1 Introduction 114
• 5.2 Experimental section 119
• 5.2.1. Materials 119
• 5.2.2. Materials Characterization 121
• 5.2.3 Fabrication of Electrodes 122
• 5.2.4 Electrocatalytic Measurements 123
• 5.3. Results and discussion 129
• 5.3.1. Morphological characterization 129
• 5.3.2. Analytical characterization 131
• 5.3.3. Electrocatalytic analysis 138
• 5.4 Conclusion 150
• 5.5 References 151
• CHAPTER 6 Conclusion 159
• 6.1. Conclusion 160
• 6. 2. Future perspectives 161
• 6.3. Appendix 163