Mechanistic study of uncatalyzed and catalyzed oxidation of Amino Acids in Aqueous acid medium

261 Pages·2016·3.23 MB·English

Mechanistic study of uncatalyzed and
catalyzed oxidation of Amino Acids
in Aqueous acid medium

A THESIS
Submitted to
UNIVERSITY OF KOTA, KOTA

for the award of

Ph. D. Degree
In Chemistry
(Faculty of Science)

Submitted by:
Shanu Mathur

Under the Joint Supervision of

Supervisor Co-supervisor
Dr. (Mrs.) Vijay Devra Dr. Manju Bala Yadav
Department of Chemistry Department of Chemistry
Govt. J.D.B. P.G. Girls College, Government College,

Kota (Raj.) Kota (Raj.)
2016
UNIVERSITY OF KOTA, KOTA

M.B.S. Marg, Near Kabir Circle, Rawatbhata Road,
KOTA (RAJ.)

Certificate

It is to certify that the

(i) The thesis entitled “Mechanistic study of uncatalyzed and
catalyzed oxidation of Amino Acids in Aqueous acid
medium” submitted by Shanu Mathur is an original piece of
research work carried out under my supervision.
(ii) Literary presentation is satisfactory and the thesis is in a form
suitable for publication.
(iii) Work evidences the capacity of the candidate for critical
examination and independent judgment.
(iv) Fulfills the requirement of the ordinance relating to the Ph.D.
degree of the university.
(v) Candidate has put in at least 200 days of attendance every year.

Dr. (Mrs.) Vijay Devra Dr. Manju Bala Yadav
Department of Chemistry, Department of Chemistry,
Govt. J.D.B. P.G. Girls College, Govt. College,
Kota (Raj) Kota (Raj)
A WORD OF GRATITUDE

“The essence of all beautiful art, all great art, is gratitude.”

My utmost gratitude goes to my thesis supervisors, Dr. Vijay
Devra and Dr. Manju Bala Yadav for allowing me to join their team, for
their expertise guidance, valuable assistance, determination, inspiration
and most of all, for their patience. I believe that one of the main gains of
this three years programme was working with them and gaining their
trust and friendship.

(Shanu Mathur)
ACKNOWLEDGEMENT

This thesis is the end of my journey in obtaining my Ph.D. I have not
travelled in a vacuum in this journey. This thesis has been kept on track and been
seen through completion with the support and encouragement of numerous people
including well wishers, my friends, colleagues and various institutions.
It is a great pleasure to convey my deep gratitude to Dr. (Mrs.) Vijay Devra,
Lecturer, Department of Chemistry, Govt. J.D.B. P.G. Girls College, Kota Rajasthan
for providing me unflinching encouragement, advice, guidance and support in
various ways. I am very much impressed with her devotion, dedication, sincerity and
modesty. Her generous help, indispensable cooperation, constructive criticism and
intellectual guidance made this work possible. She has been not only inspiring
mentor but also gain my respect for her affectionate and kind behavior. I am
sincerely grateful to God for giving me an opportunity to work with such an
excellent mentor, I am indebted to her more than she knows.
I would like to convey sincere gratitude to my co-supervisor Dr. Manju Bala
Yadav, Department of Chemistry, Govt. College, Kota for her inspiration and
valuable guidance genuine interest, continuous encouragement, valuable suggestion
to bring this work into desired state.
I would like to expand my thanks to Prof. Ashu Rani (Professor, Department
of Pure and Applied Chemistry, University of Kota, Kota Rajasthan) for her
inspiring guidance and generous support.
At this moment of accomplishment, I take this opportunity to sincerely
acknowledge Dr. Pankaj Kachhawah and Mr. Rajesh Yadav for their cooperation
and moral support.
I express a lage debt of gratitude to Mrs. Jagriti Sharma, Principal and
Dr. Uma Sharma, Head, Department of Chemistry, Govt. J.D.B. P.G. Girls College,
Kota for personal guidance, motivation and for extending facilities available in the
college during my research work.
I would like to express my sincere and deepest appreciation to Dr. Naveen
Mittal, Dr. Arti Shah, Dr. Saraswati Agarwal and all faculty members of depart-
ment of chemistry, Govt. J.D.B. P.G. Girls College, Kota who have been very kind
enough to extend their help at various faces of this research, whenever I approach
them, and I do hereby acknowledge all of them. I thank my lab mates Renu Hada,
Khushboo Shrivastava, Shikha Jain, Ankita Jain, Niharika Nagar, Gajala
Tazwar, Priya Vijay and Dhanraj Meena for their valuable suggestions in experi-
mentation and their cooperation during the entire research work.
I am extremely grateful to Mr. Dinesh Vijay, Director, M.B. Group of
Education, Dr. Prem Jain, Principal, M. B. P.G. College, and convey special
acknowledge to my colleagues Dr. Shweta Saxena, Dr. Sushila Joshi, Archana
Goyal, Dr. Bharati Sharma, Vinita Sharma, Meenakshi Sharma, Dr. Nivedita
Sharma, Nandini Sharma, Purushottam Sharma Sir and all other staff members
of M. B. P.G. College, Kota. I wish I could mention each individually refreshing me
and encourage me.
I express thanks to my Hubby “Brijesh” who has helped me to nurture an
environment of creativity and support. It was he only who always stood besides me
during all the moments and shades of life. It is once against the matter of expressing
emotions, feeling gratitude in available few limited words. These words don’t
represents my expression, devotions and respect to my partner. Special thanks to my
son Sahil for his support.
I would like to express a debt of gratitude to my father-in-law late Sh. D. S.
Mathur, mother-in-law Mrs. Sushila Mathur, brother-in-law Mr. Dinesh Mathur,
bhabhi Mrs. Purnima Mathur, brother-in-law Mr. Yogesh Mathur and sister-in-
law Mrs. Meenakshi Mathur and Mohit, Abhay(nephew), Yamini, Gunjan
(niece) for their kind support, love patience and constant which made it possible to
reach my goal.
I really feel indebted to my parents, my father Mr. N.B. Mathur, mother
Mrs. Vimla Mathur, sisters Anju di, Ranu di, Neelu and Rani and all my Jiyaji
Mr. P. B. Mathur, Mr. D. C. Rai, Mr. Rakesh Mathur and Mr. Neeraj Mathur
and my brother Dr. Hemant Mathur, bhabhi Dr. Aditi Mathur who always
extended their best cooperation towards me, which made me go steadily and firmly
through the ups down of this entire period. Their moral and friendly support brought
this process of this study to culminate successfully.
Most importantly, none of this would have been possible without the love and
patience of my family. My immediate family to whom this thesis is dedicated to, has
been a constant of source of love, concern, support and strength of these years. My
entire family has aided and encouraged me through this endeavor. I warmly
appreciate the generosity and understanding of each one of them.
I also want to give lot of thanks to Mr. Vimal Handa for his dedication
towards the formatting and typing of this thesis.

(Shanu Mathur)
I dedicate this thesis to
my family, husband ‘Brijesh’
and beloved son ‘Sahil’
for their constant support
and unconditional love.
CONTENTS

Chapters Title Page No.

1 Introduction 1 – 48
Abstract 1
1.1 Catalysis and Mechanism 3
1.2 Cerium(IV) – An Oxidant 4
1.2.1 Kinetic Studies with cerium(IV) 8
1.3 Chromium(VI) – An Oxidant 8
1.3.1 Kinetic Studies with chromium(VI) 9
1.4 Metal ion catalysis 12
1.4.1 Mn(II) – A Catalyst 13
1.4.2 Silver(I) – A Catalyst 15
1.5 Amino Acids 18
1.6 Oxidation of Amino Acids 21
1.7 Scope of the work 30
1.8 References 32
2 Experimental 49 – 56
Abstract 49
2.1 Chemicals 50
2.2 Equipments 53
2.3 References 56
3 Mechanistic and Kinetic Study of 57 - 92
Oxidation of Lysine by Chromium(VI)
in Perchloric Acid Medium
Abstract 57
3.1 Introduction 58
3.2 Experimental 58
3.3 Results 61
3.4 Discussion 83
3.5 Conclusion 90
3.6 References 91
4 Mechanistic and Kinetic Study of 93 - 122
Oxidation of Threonine by Chromium(VI)
in Perchloric Acid Medium
Abstract 93
4.1 Introduction 94
4.2 Experimental 95
4.3 Results 96
4.4 Discussion 115
4.5 Conclusion 120
4.6 References 121
5 Mechanistic and Kinetic Study of 123 - 155
Mn(II) Catalyzed Oxidation of Alanine
by Cerium(IV) in Sulphuric Acid Medium
Abstract 123
5.1 Introduction 124
5.2 Experimental 125
5.3 Results 128
5.4 Discussion 146
5.5 Conclusion 153
5.6 References 154
6 Mechanistic and Kinetic Study of 156 - 194
Uncatalyzed and Ag(I) Catalyzed
Oxidation of Serine by Cerium(IV)
in Acid Perchlorate Medium
Abstract 156
6.1 Introduction 157
6.2 Experimental 158
6.3 Results 160
6.4 Discussion 176
6.5 Conclusion 191
6.6 References 192
Annexure – I
Annexure – II
Publications