By Priyanka Karolia - Shodhgangashodhganga.inflibnet.ac.in/bitstream/10603/111223/1/1...Priyanka Karolia Chapter 1: General Introduction 1-45 1. Surfactants: Application in Electrochemistry

A

THESIS

SUBMITTED FOR THE DEGREE OF

DOCTOR OF PHILOSOPHY

IN

CHEMISTRY

Prof. Rajeev Jain Prof. D.C. Tiwari

SCHOOL OF STUDIES IN CHEMISTRY JIWAJI UNIVERSITY, GWALIOR (M.P.)

2015

By

Priyanka Karolia

PREPARATION AND CHARACTERIZATION OF POLYMER

NANOCOMPOSITE SENSOR FOR ELECTROCHEMICAL

STUDIES OF SOME PHARMACEUTICALS

Under the Supervision of

Dedicated to my parents Dedicated to my parents Dedicated to my parents Dedicated to my parents

When the worldclosed its door on me, you opened your arms for me. When people shut their ears for me, you opened your hearts for me. Mom and dad, thanks for always being there for me.

When the worldclosed its door on me, you opened your arms for me. When people shut their ears for me, you opened your hearts for me. Mom and dad, thanks for always being there for me.

When the worldclosed its door on me, you opened your arms for me. When people shut their ears for me, you opened your hearts for me. Mom and dad, thanks for always being there for me.

When the worldclosed its door on me, you opened your arms for me. When people shut their ears for me, you opened your hearts for me. Mom and dad, thanks for always being there for me.

"

itself to light the way for others''

A teacher is just like a candle it consumes

You blessed me with success. You gave

me the power to believe in myself & pursue my dreams.

I consider myself lucky to have you as my mentor & guide.

A Word of Gratitude

DECLARATION

I hereby declare that the thesis entitled “Preparation and

Characterization of Polymer Nanocomposite Sensor for Electrochemical

Studies of Some Pharmaceuticals” is my own work conducted under the

supervision of Prof. D.C. Tiwari and Prof. Rajeev Jain, at School of Studies in

Chemistry, Jiwaji University, Gwalior, (M.P.) India, approved by Research

Degree Committee, I have put in more than 200 days of attendance with the

supervisors at the centre.

I further declare that to the best of my knowledge the thesis does not

contain any part of any work, which has been submitted for the award of any

degree either in this University or in any other University/Deemed University

without proper citation.

Signature of the Candidate

Priyanka Karolia

School of Studies in Chemistry

Jiwaji University, Gwalior (M.P.)

Signature of the Supervisors

Prof. D.C. Tiwari Prof. Rajeev Jain

School of Studies in Physics School of Studies in Chemistry

Jiwaji University, Gwalior (M.P.) Jiwaji University, Gwalior (M.P.)

Forwarded

Signature of Head of the Department

0751-2442769

SCHOOL OF STUDIES IN CHEMISTRY (DST-FIST Sponsored)

JIWAJI UNIVERSITY, GWALIOR – 474 011 (M.P.) INDIA

CERTIFICATE

This is to certify that the work entitled “Preparation and Characterization

of Polymer Nanocomposite Sensor for Electrochemical Studies of Some

Pharmaceuticals” is a piece of research work done by Ms. Priyanka Karolia

under our guidance and supervision for the degree of Doctor of Philosophy in

Chemistry, in Jiwaji University, Gwalior (M.P.). The candidate has put in an

attendance of more than 200 days with us.

To the best of our knowledge and belief the thesis:

Embodies the work of the candidate herself,

Has duly been completed,

Fulfills the requirements of the ordinance relating to the Ph.D. degree of

the University and

Is up to the standard, both in respect of contents and language for being

referred to the examiner.

Signature of the Supervisors

Prof. D.C. Tiwari Prof. Rajeev Jain

School of Studies in Physics School of Studies in Chemistry

Jiwaji University, Gwalior Jiwaji University, Gwalior

Forwarded

Signature of Head of the Department

ACKNOWLEDGEMENTS

“The light at the end of the tunnel may be dark, it's up to you to make it brighter -you have to help

yourself and your goals first, before God can help you”

I glorify the almighty God for his countless blessing, which enabled me to complete this endeavor

fruitfully. I would take this opportunity to praise divine power whose unceasing intercession provided me

the strength, courage and wisdom into this maneuver.

This thesis is the end of my journey in obtaining my Ph.D. I have not traveled in a vacuum in this journey. This thesis has been kept on track and been seen through to completion with the support and encouragement of numerous people including my well wishers, my friends, colleagues and various institutions. At the end of my thesis I would like to thank all those people who made this thesis possible and an unforgettable experience for me. At the end of my thesis, it is a pleasant task to express my thanks to all those who contributed in many ways to the success of this study and made it an unforgettable experience for me. At this moment of accomplishment, first of all I pay homage to my guide, Prof. Rajeev Jain, School of Studies in Chemistry, Jiwaji University, Gwalior (M.P.). This work would not have been possible without his guidance, support and encouragement. Under your guidance, I successfully overcame many difficulties and learned a lot. I sincerely thank for his encouragement and direction that inspired me to take the right path. He was very affectionate and was ready to help me even in the midst of his busy schedule. I can no other answer make, but, thanks, thanks and thanks.

I want to express my deep thanks to my esteemed promoter Prof. D.C. Tiwari, School of Studies in Physics, Jiwaji University, Gwalior for the trust, the insightful discussion, offering valuable advice, his support during the whole period of the study, and especially for his patience and guidance during the writing process. I am very much thankful to him for picking me up as a student at the critical stage of my Ph.D.

I convey my regards and heartfelt respect to Dr. Anupam Jain for her kind support, inspiration, guidance and motherly care throughout my research work.

I take this opportunity to sincerely acknowledge the Department of Science and Technology (DST), Government of India, New Delhi, for providing financial assistance in the form of Junior Research Fellowship which buttressed me to perform my work comfortably.

I wish to express my deep sense of gratitude to Prof. S.K. Srivastava, Professor and Head, School of Studies in Chemistry, Jiwaji University, for providing me all possible facilities required to complete this venture.

My gratitude also goes to all the respected teachers Prof. C.P. Shinde, Prof. K.K. Dwivedi, Prof. A.K. Halve, Prof. S.K. Gupta, Prof. D.D. Agarwal & Prof. Radha Tomar Department of Chemistry, Jiwaji University, who gave me valuable inputs to lend weight to my research. I would also like to

thank Dr. Nimisha Jadon (Assistant Professor), Prof. R.K. Tiwari and Prof Raja Ram Sir for their

valuable advices and timely suggestions.

I convey my regards and heartfelt respect to Dr. Shalini Sikarwar for her kind support, inspiration, guidance and motherly care throughout my research work.

My sincere thanks are also to my seniors Dr. Garav Sahu, Dr. Shraddha Sharma, Dr. Vikas, Dr.

Ramkishor Sharma, Dr. Sanjay Sharma, Dr. Dhanjay, Dr. Ambika Chopra, Dr. Rati Jain and Dr.

Nirupama Guru Aribam, for their kind suggestions during this tenure.

I am indebted to my colleagues for providing a stimulating and fun environment to learn and grow. I am especially grateful to research scholars Dr. Pooja Sharma, Mr. Satyendra Kadam, Mr. Lateef Khan, Ms. Swati Goyal and Ms. Ankita Sinha at Jiwaji University. I ove a debt of gratitude to all my friends who encouraged me at every stage of work especially Dr. Swati Shrivastava and Dr. Preeti Pandey for their generous help and constructive suggestions during the entire course of this work. My endeavour would have remained incomplete without the blessings and unending support of my family members. At this moment I also want to remember my grandfather (Baba) late Mr. Ram Das Karolia. I know that from the seventh sky you are watching me doing all and showering your blessings on me. As any achievement of my life is a result of my mother Mrs. Rajkumari Karolia & my father Mr. Ashok Kumar Karolia efforts & blessings and without that I could not be able to make it happens at all. Their encouragement, support and guidance are the key element of my performance, success and achievements. This page will be incomplete without expressing feeling from bottom of heart towards my father in-law Mr. Arun Tripathi and late Mrs. Tara Tripathi for understanding and support me. They are always with me in my dreams and in action, their life and teaching have always been a source of inspiration to me in the journey of my life, which has no destination. Also I express my thanks to my sister, brother, sister in law and brother in law and innocent love of

master Ayan Tripathi for their love, good wishes, encouragement and support throughout my research

work.

My special thanks to most precious part of my life, my soul, my love, my Son Vivan Tripathi, and to the man who is the pillar of strength in my life without him my hard work would not have materialise my husband Mr. Ashish Tripathi who have supported and guided me in all the challenges I faced in the tenure of my PhD.

I am thankful to the non-teaching staff of Department of Chemistry, Jiwaji University. Finally I wish to thank everyone who has been directly or indirectly helped by nudging me towards this

achievement.

Priyanka Karolia

Chapter 1: General Introduction 1-45

1. Surfactants: Application in Electrochemistry

2. Electrochemical Sensor

2.1 Potentiometric Sensor

2.2 Amperometric Sensor

2.3 Conductometric Sensor

3. Types of Voltammetry

3.1 Non Stripping Techniques

3.2 Stripping Techniques

4. Instrumentation

4.1 Potentiostat

4.2 Electrochemical Cell

5. Nanomaterials

6. Polymer Nanocomposite

7. Solvents and Supporting Electrolyte

8. Analytical Method Validation

9. Scope of Research

10. References

Chapter 2: Highly Sensitive and Selective Polyaniline–Zinc Oxide 46-67

Nanocomposite Sensor for Betahistine Hydrochloride in Solubilized System

1. Introduction

2. Experimental

2.1 Chemical and Reagents

2.2 Apparatus and Measurements

2.3 Preparation of PANI-ZnO Nanocomposite Sensor

2.4 Fabrication of PANI-ZnO Modified Glassy Carbon Electrode

3. Results and Discussion

3.1 Characterization of Fabricated Sensor

3.2 Effect of pH

3.3 Betahistine Hydrochloride Behaviour in Solubilized System

3.4 Cyclic Voltammetric Behaviour of Betahistine Hydrochloride

3.5 Electrocatalytic Performance of PANI-ZnO/GCE Hybrid Film Sensor

3.6 Reproducibility and Stability of Modified Electrochemical Sensor

3.7 Calibration Curve and Limit of Detection

3.8 Recovery

Declaration

Certificate

Acknowledgement

Abbreviations

CONTENTS

3.9 Analytical Application

4. Conclusion

5. References

Chapter 3 : Electrocatalytic Detection and Quantification of 68-90

Nitazoxanide Based on Graphene-Polyaniline (GRP-PANI) Nanocomposite

Sensor

1. Introduction

2. Experimental

2.1 Chemical and Reagents

2.2 Apparatus and Measurements

2.3 Preparation of Polyaniline

2.4 Fabrication of PANI-GRP/GCE Hybrid Film Sensor

3. Results and Discussion

3.1 Characterization of Fabricated Sensor

3.2 Optimization of Variable Parameter

3.3 Electrocatalytic Performance of PANI-GRP/GCE Hybrid Film Sensor

3.4 Calibration Graph and Detection Limit

3.5 Repeatability of Modified Electrochemical Sensor

3.6 Reaction Mechanism for Nitazoxanide Reduction

3.7 Recovery and Interference Study

3.8 Analytical Application

4. Conclusion

5. References

Chapter 4: Electrocatalytic Sensing of Omeprazole 91-112

1. Introduction

2. Experimental

2.1 Chemicals and Reagents

2.2 Apparatus and Measurements

2.3 Preparation of PANI-MWCNTs Nanocomposite Sensor

2.4 Fabrication of PANI-MWCNTs/GCE Hybrid Film Sensor

3. Results and Discussion

3.1 Characterization of Fabricated Sensor

3.2 Optimization of Variable Parameters

3.3 Scan Rate Studies

3.4 Electrocatalytic Performance of PANI-MWCNTs/GCE Hybrid Film Sensor 3.5 Repeatability of Modified Electrochemical Sensor

3.6 Calibration Curve and Limit of Detection

3.7 Recovery

3.8 Analytical Application

4. Conclusion

5. References

Chapter 5: Polyaniline-Zinc oxide Composite Glassy Carbon Sensor 113-129

For Electrocatalytic Determination of Gastric Acid Inhibitor Pantaprazole

1. Introduction

2. Experimental

2.1 Chemicals and Reagents

2.2 Apparatus and Measurements

2.3 Preparation of PANI-ZnO Nanocomposite Sensor

2.4 Fabrication of PANI-ZnO Modified Glassy Carbon Electrode

3. Results and Discussion

3.1 Characterization of Fabricated Sensor 3.2 Optimization of Variable Parameters

3.3 Electrocatalytic Performance of PANI-ZnO/GCE Hybrid Film Sensor

3.4 Reproducibility and Stability of Modified Electrochemical Sensor

3.5 Calibration Curve and Limit of Detection

3.6 Recovery

3.7 Analytical Application

4. Conclusion

5. References

Summary i-v

List of Publications

CV Cyclic Voltammetry

DPV Differential Pulse Voltammetry

SWV Square Wave Voltammetry

ASV Anodic Stripping Voltammetry

CSV Cathodic Stripping Voltammetry

AdSV Adsorptive Stripping Voltammetry

SWCADSV Square-Wave Cathodic Adsorptive Stripping Voltammetry

BR Britton Robinson

SEM Scanning Electron Microscopy

HMDE Hanging Mercury Dropping Electrode

DME Dropping Mercury Electrode

CMEs Chemically Modified Electrodes

GCE Glassy Carbon Electrode

LSV Linear Sweep Voltammetry

NPV Normal Pulse Voltammetry

HPLC High Performance Liquid Chromatography

RP-HPLC Reverse Phase High Performance Liquid Chromatography

MWCNTs Multiwalled Carbon Nanotubes

ZnO Zinc Oxide

MWCNTs/GCE Multiwalled Carbon Nanotubes Modified Glassy Carbon Electrode

GRP Graphene

PANI Polyaniline

PANI-ZnO Polyaniline-Zinc Oxide

OMP Omeprazole

DMF N, N-dimethylformamide

CAN Acetonitrile

CTAB Cetyltrimethylammonium Bromide

T-20 Tween-20

KCl Potassium Chloride

SLS Sodium Lauryl Sulphate

PANI-ZnO/GCE Polyaniline-Zinc Oxide Modified Glassy Carbon Electrode

PANI/GCE Polyaniline Modified Glassy Carbon Electrode

PANI-GRP Polyaniline-Graphene

PANI-GRP/GCE Polyaniline-Graphene Modified Glassy Carbon Electrode

GRP/GCE Graphene Modified Glassy Carbon Electrode

PANI-MWCNTs Polyaniline-Multiwalled Carbon Nanotubes

PANI-MWCNTs/GCE Polyaniline-Multiwalled Carbon Nanotubes Modified Glassy

Carbon Electrode

LOD Limit of Detection

LOQ Limit of Quantification

RSD Relative Standard Deviation

ABBREVIATIONS