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Title
DEDICATION
CERTIFICATE
DECLARATION
ACKNOWLEDGEMENT
List of Notations and Abbreviations
CONTENTS
1. Introduction
1.1 Organisation of the thesis
2. Polymer-supported Metal Complexes as Catalysts: A Retrospect.
2.1 Classification of Polymer-metal Complexes
2.1.1 Polymer-metal complexes: Synthesis and classification
2.1.1.1 Pendant metal complexes
(a) Monodentate pendant complexes
(b) Polydentate pendant complexes
2.1.1.2 Inter- and intra-molecularly bridged polymer-metal complexes.
2.1.1.3 Polymerisation of coordinated monomers
2.1.2 Reaction of Peripheral Functional Groups in Metal Complexes with Polymers
2.1.3 Structure and Reactivity
2.1.4 Coordination Polymers
2.1.4.1 Linear coordinated polymers
2.1.4.2 Network-coordinated polymers (Parquet)
2.1.5 Application of polymer-metal complexes
2.1.5.1 Ion selectivity
2.1.5.2 Catalytic activity
2.1.6 Polymer-metal Complexes as Heterogeneous Catalysts
2.1.7 Macromolecular Effects on Catalytic Activities of Polymer-metal Complexes
2.1.7.1 Nature of support and cross linking
2.1.7.2 Porosity and surface area
2.1.7 3 Swelling and salvation of the macromolecular matrix
2.1.7.4 Effect of spacers
3. Synthesis and Characterisation of Polystyrene-supported Glycine-metal Complexes
3.1 Synthesis of 2 mol% DVB-, EGDMA- and HDODA-cross linked Polystyrene-supported Glycines
3.1.1 Preparation of DVB-, EGDMA- and HDODA-cross linked polystyrenes.
3.1.2 Incorporation of Glycine Function on Cross linked Polystyrene
3.2 Complexation Behaviour of Various Polystyrene-supported Glycines
3.2.1 Effect of the nature of cross linking agent on complexation
3.2.2 Influence of pH on metal ion binding
3.3 Characterisation of Polymeric Ligands and their Metal Complexes
3.3.1 13C CP-MAS NMR Spectra
3.3.2 FTIR Spectra
3.3.3 UV-visible Spectra
3.3.4 EPR Spectroscopy
3.3.5 Thermogravimetric Analysis
3.3.6 Scanning Electron Microscopy
3.4 Swelling Studies
4. Synthesis and Characterisation of N.Vinyl-2-Pyrrolidone-Acrylic Acid Copolymers and their Metal Complexes
4.1 Preparation of Linear and 4 mol% DVB-, EGDMA- and HDODA-cross linked N-vinyl-2-pyrrolidone-acrylic Acid Copolymers
4.2 Metal ion complexation of various NVP-AA copolymers
4.2.1 Influence of pH on metal ion complexation of NVP-AA copolymers
4.3 Characterisation of Polymeric Ligands and Derived Polymer-metal Complexes
4.3.1 13C CP-MAS NMR Spectra
4.3.2 FTIR Spectra
4.3.3 UV-visible Spectra
4.3.4 EPR Spectra
4.3.5 Nitrogen Analysis
4.3.6 Themogravimetric Analysis
4.3.7 Scanning Electron Microscopy
4.4 Swelling Studies of Various Cross linked NVP-AA copolymers
5. Catalase-like Activity of Polystyrene-, and M-vinyl-2-pyrrolidone Acrylic Acid Copolymer-supported Metal Complexes
5.1 Polystyrene Systems
5.1.1 Catalytic activity of DVB-cross linked polystyrene-supported glycine-metal complexes
5.1.2 Catalytic activity of EGDMA-cross linked polystyrene-supported glycine-metal complexes
5.1.3 Catalytic activity of HDODA-cross linked polystyrene-supported glycine-metal complexes
5.1.4 Kinetics of hydrogen peroxide decomposition by polystyrene-supported Sodium salt of glycine-Cu (ll) complexes
5.1.5 Effect of the nature of cross linking agent on the decomposition of hydrogen peroxide
5.2 N-VinyI, Z-Pyrrolidone-Acrylic Acid Copolymer Systems
5.2.1 Catalytic Activity of DVB-cross linked NVP-AA Copolymer-metal Complexes
5.2.2 Catalytic Activity of EGDMA-cross linked NVP-AA Copolymer-metal Complexes
5.2.3 Catalytic Activity of HDODA-cross linked NVP-AA Copolymer-metal Complexes
5.2.4 Catalytic Activity of Linear NVP-AA Copolymer-metal Complexes
5.2.5 Kinetics of Hydroygen Peroxide Decomposition by NVP-AA Copolymer-Co (II) Complexes
5.2.6 Effect of Cross linking Agent on the Decomposition of Hydrogen Peroxide.
5.2.7 Effect of Various Parameters on the Catalytic Decomposition of Hydrogen Peroxide
5.2.8 Recyclability
6. Experimental
6.1 General
6.1.1 Materials
6.1.2 Instrumental
6.2 Synthesis of 2 mol% DVB-, EGDMA- and HDODA-cross linked polystyrene-supported glycine
6.2.1 Preparation of 2 mol% DVB-, EGDMA- and HDODA-cross linked Polystyrenes: General Procedure
6.2.2 Incorporation of Gtycine Function on Cross linked Polystyrenes.
6.3 Preparation of Sodium Salt of Linear and 4 mol% DVB-, EGDMA-, any HDODA-cross linked N-Vinyl-2-Pyrrolidone--Acrylic Acid Copolymers ii
6.3.1 Synthesis of Linear and 4 mol% DVB-, EGDMA-, and H DO DA-cross linked NVP-AA Copolymers
6.3.2 Derivatisation of Linear and Cross linked NVP-AA Copolymers.
6.4 Preparation of Polymer-metal Complexes: General Procedure
6.5 pH Dependence on Metal Ion Binding: General Procedure
6.6 Swelling Studies: General Procedure
6.7 Catalytic Activities of Polymer-supported Metal Complexes: General Procedure
7. Summary and Outlook
References