BSc MSc Bihar , PhD IIT Kanpur
Current Research Interests: We have been working in the following areas of research:
Kinetic Methods of Analysis/Analytical and Environmental Chemistry
My research group and I are interested in understanding the kinetics of ligand substitution reactions of transition metal compounds with particular emphasis on their application as analytical tool. Our investigations are aimed at building mechanistic understanding of ligand substitution as well as oxidation reactions that can advance our knowledge of catalytic kinetic methods (CKMs). We determine catalysed and uncatalysed reaction mechanisms by studying chemical kinetics and apply such reactions for the development of inexpensive analytical methods for trace determination of toxicants, environmental pollutants and species of biological interest.
The development of methods for determination of toxic species, environmental pollutants and species of biological interest at trace level is challenging analytical expertise especially for complex samples. The specialized instrumentation needed for trace analysis and the associated procedures involved are often very expensive. The “Kinetic Methods of Analysis” (also called Reaction Rate Methods) utilising spectrophotometric monitoring is an inexpensive analytical method. The CKM continues to be the most popular method in the literature of Kinetic Methods of Analysis. My research group is involved in the developments of CKMs for trace determination of toxicants, environmental pollutants and species of biological interest. It has been demonstrated that it is possible to determine catalytic or inhibitor species (environmental pollutants, toxicants or species of biological interest) by measuring their effects on reaction rates, down to ppm/ppb levels. The cost effective CKMs for the determination of Hg2+, Cu2+, Se2+, Se4+, Ru3+, cysteine, thiosulphate, MNDT (S2C2(CN)22-), NO3-, NO2- etc. in environmental and vegetables samples have been developed using different indicator reactions. The methods are simple, sensitive, selective and economical compared to AAS, radio-istope techniques, mass spectrometry, activation analysis, etc. The undertaken research projects are intended to study regional environmental problems and to develop professional manpower in the area of development of cost-effective analytical techniques. Hence we have been working on the following research projects:
i. Development of catalytic kinetic method for trace determination of mercury(II).
Along with understanding the kinetics and mechanism of ligand substitution/oxidation reactions a CKM is being proposed for ascertaining the trace levels of toxic mercury(II). The method being developed is to be tested for determination of mercury(II) in the real water samples like waters of Fiji.
ii. Chemical and biological monitoring of selective heavy metal species in inland, coastal waters and soils samples in Viti Levu (Fiji).
This is a collaborative research project with Dr. Rajendra Prasad (Chemistry Division) and Mr. Waisea Votadroka (Institute of Applied Sciences) of the University of the South Pacific and Prof. P.K. Dasgupta, Chairman, Department of Chemistry and Biochemistry, University of Texas, Arlington (UTA), TX, USA.
iii. Studies on adsorptive removal of nephrotoxic heavy metals from aqueous solutions and contaminated natural waters.
This is a collaborative study in which senior chemistry staff member, Dr. Rajendra Prasad, of the University of the South Pacific is involved.
Multi-step Ligand Exchange/Oxidation Reactions
I have made significant contributions towards enhancing understanding the mechanism of ligand exchange reactions. I have succeeded in studying the reaction dynamics of relatively slow as well as fast (t˝ = m sec.) reactions and in unraveling the mechanistic features of the reactions occurring in four, five and six steps. The kinetics and mechanism of ligand exchange reactions involving polydentate ligands viz. aminopolycarboxylates, polyamines, polychromics coordinated to Mn(III), Fe(III), Zn(II) and Ni(II) centres by cyanide ions and PAR have been investigated. All these reactions follow variable order dependence in cyanide. The reverse rate is first order in M(CN)x [x = 4, 5, 6; M = metal] and first order in L [L = ligand] and exhibit an inverse first order dependence in [CN-]. These results led us to postulate a multi-step mechanistic scheme in which cyanide ions add one by one to the vacant sites generated by the progressive unwrapping of the ligand coordinated to the metal centres.
Besides, the kinetics of catalysed and uncatalysed monodentate ligand exchange reactions of hexacyanoferrate(II) complex with N-methylpyrazinium ion (Mpz+), α-nitroso β-naphthol, pyrazine, 2-methyl pyrazine (2Mepz), etc. are being investigated followed by their application as analytical tool.
In addition to above areas of research, we have been working on the following projects:
i. Exposure to cadmium and arsenic via leafy vegetables in Fiji. This is a collaborative study in which senior chemists of the University of the South Pacific, Dr. Rajendra Prasad.
ii. Study of the effects of cooking and deep-freezing on the nitrate concentration in Fiji’s vegetables using flow injection analysis (FIA).
iii. Application of catalytic kinetic method to ascertain the contents of nitrite in water and vegetables samples in Fiji.
The flow injection analysis (FIA) and spectrophotometeric techniques have been developed to determine NO3- and NO2- respectively in vegetables and water samples. The methods are being applied to the determination of NO3- in commonly consumed leafy, fruit and root vegetables of Fiji.
Synthesis, Characterization, Antibacterial and Antifungal Studies of Inorganic Complexes
To discover the antibacterial and antifungal properties of inorganic complexes, we have been working on the following research projects:
i. Synthesis of new molecular receptors based on polypyridyl-ruthenium(II) linked metallo-macrocycles. This is a collaborative study in which senior chemists of the University of the South Pacific, Dr. Rajendra Prasad.
ii. An Investigation on Chelating Behavior of Heterocyclic Semicarbazones toward Bioactive Metal ions.
iii. An Investigation on Structure and Bonding in Some High Coordinated Complexes of Thorium(IV) and Dioxouranium(VI) Derived from Heterocyclic Semicarbazones as Primary Ligand and Diphenyl Sulfoxide as Secondary Ligand.
A series of mono- and binuclear ruthenium complexes of the type [Cp(EPh3)RuL]-/+, [(bipy)2RuL]0/2+, [Ru2Cp2(EPh3)4L], [Ru2Cp2(EPh3)3L] 2+ and [Ru2Cp(EPh3)2(bipy)2]+/3+ [E = P, As, Sb; L = S2C2(CN)22- or (C6H5CH2)S2C2(CN)2] have been synthesized exploiting the nucleophilicity of S and N in L. The complexes have been characterized by microanalysis, conductance, IR, 1H and 31P NMR and UV-visible spectral data.
Also synthesis magneto-spectral and thermal characteristics of some lanthanide(III) chloro complexes derived from 4[N-(4’-hydroxy-3’-methoxybenzalidene)amino]antipyrine semicarbazone; 4[N-(3’,4’,5’trimethoxy-benzalidene)amino]antipyrinesemicarbazone; 4[(furan-2-ylmethylene)amino]-1,5-dimethyl-2-phenylpyrazol-3-one; isonicotinic acid(3’,4’,5’-trimethoxybenzylidene)hydrazide and some mixed ligand complexes of thorium(IV) and dioxouranium(VI) with semicarbazones as primary ligand and sulfoxide as secondary ligand and penta-coordinated complexes of oxovanadium(IV) derived from thiosemicarbazones of 4-aminoantipyrine have been carried out. Besides these, synthesis and spectral investigations of some platinum metals ions coordination compounds of 4[N-(furan-2-carboxalidene)-amino]antipyrine thiosemicarbazone and 4[N-(3’,4’,5’-trimethoxybenzalidene)amino]antipyrine thiosemicarbazone has been carried out. Also, synthesis, magneto-spectral, biological and thermal investigations of cobalt(II) and nickel(II) coordination compounds of thiosemicarbazones derived from 4-aminoantipyrine and hydrazones of isonicotinic acid hydrazide has been done. It has been established that many of the complexes studied have potent antibacterial and antifungal properties/activities.
1. Rajendra Prasad, Rajeev Kumar and Surendra Prasad; A Fluorescence Quenching-based Sensor Using New Metallo-tetraazaporphyrin Dye as a Recognition Element for Aniline Assay in Aqueous Solutions. Anal. Chim. Acta (Elsevier) 646 (1-2), 97-103, 2009.
2. Radhey M. Naik, Abhinav Agarwal and Surendra Prasad; Ligand Substitution Reaction of Hexacyanoruthenate(II) as a Tool for Mercury(II) Estimation at Micro Level. Spectrochim. Acta Pt. A: Mol. Biomol. Spectrosc. (Elsevier), 74 (4), 887-891, 2009.
3. Surendra Prasad and Ram K. Agarwal; Nickel(II) Complexes of Hydrazones of Isoniazid and Their Magneto-spectral, Electrochemical, Thermal and Antimicrobial Investigations. J. Korean Chem. Soc., 2009 (Accepted).
4. Ram K. Agarwal, Surendra Prasad and Hans Raj Modi; Synthesis, Spectral and Thermal Properties of Some Novel Coordination Compounds of VO(IV) Derived from 4[N-(4˘-Ethylbenzalidene)Amino]Antipyrine Thiosemicarbazone and 4[N-(2˘,4˘-Dimethyl Benzalidene)Amino]Antipyrine Thiosemicarbazone, Journal of the Iranian Chemical Research (Ms. Ref. No.: JICR-09-00013) 2009 (Accepted).
5. Radhey M. Naik, Abhinav Agarwal, Surendra Prasad and Amit K. Verma; Trace Determination of Thiosulphate and Thioglycolic Acid Using Novel Inhibitory Kinetic Spectrophotometric Method. Microchem. J. (Elsevier), 93(1), 43-48, 2009.
6. Adrian Avinesh Chetty and Surendra Prasad; Flow Injection Analysis of Nitrate-N Determination in Root Vegetables: Study of the Effects of Cooking. Food Chem. (Elsevier), 116(2), 561-566, 2009.
7. Vimlesh Chand and Surendra Prasad; Trace Determination and Chemical Speciation of Selenium in Environmental Water Samples Using Catalytic Kinetic Spectrophotometric Method. J. Hazardous Mat. (Elsevier), 165(1-3), 780-788, 2009.
8. Rajendra Prasad and Surendra Prasad; Spectrophotometric Method for the Determination of Fe3+-Gly Formation Constant Through Competitive Ligand Binding. J. Chem. Edu. (Am Chem. Soc., USA), 86(4), 994-997, 2009.
9. Surendra Prasad and Ram K. Agarwal; Synthesis, Physico-chemical and Biological Properties of Complexes of Cobalt(II) Derived from Hydrazones of Isonicotinic Acid Hydrazide. J. Korean Chem. Soc., 53(1), 17-26, 2009.
10. Surendra Prasad, R.M. Naik and Vimlesh Chand; Kinetics and Mechanism of Uncatalysed Exchange of Cyanide in Hexacyanoferrate(II) by N-Methylpyrazinium Ion. Inorg. React. Mech., (OCP Science, USA) 6(4), 337-344, 2008.
11. Surendra Prasad and Ram K. Agarwal, Nickel(II) Complexes of Hydrazone of Isoniazid and Their Magneto-Spectral, Electrochemical, Thermal and Antimicrobial Investigations. Research Letters in Inorganic Chemistry (Hindawi Publishing Corpn., USA) Vol. 2008 (Article ID 350921), 1-4, 2008.
12. Vipin Kumar Bansal, Rajeev Kumar, Rajendra Prasad and Surendra Prasad, Niraj; Synthesis and Spectral Characterization of New Copper(II) Macrocycle Complexes and Investigation of Their Catalytic Role in Wet Oxidation of Phenol. Journal of Molecular Catalysis A, (Elsevier), 284 (1-2), 69-76, 2008.
13. Surendra Prasad and Adrian Avinesh Chetty; Nitrate-N Determination in Leafy Vegetables: Study of the Effects of Cooking and Freezing. Food Chem. (Elsevier), 106, 772-780, 2008.
14. Radhey Mohan Naik, Joy Sarkar and Surendra Prasad; Kinetic determination of cysteine and thiosulphate by inhibition of Hg(II) catalysed ligand substitution reaction. Microchem. J. (Elsevier) 88(1), 45-51, 2008.
15. Surendra Prasad; Radhey M. Naik and A. Srivastava; Application of Ruthenium catalyzed oxidation of [tris(2-aminoethyl)amine] in trace determination of ruthenium in environmental samples. Spectrochim. Acta Pt. A: Mol. Biomol. Spectrosc. (Elsevier), 70, 958-965, 2008.
16. Radhey M. Naik; A. Srivastava and Surendra Prasad; Highly Sensitive Catalytic Spectrophotometric Determination of Ruthenium. Spectrochim. Acta Pt. A: Mol. Biomol. Spectrosc. (Elsevier), 69(1), 193-197, 2008.
17. Surendra Prasad; Kinetic Determination of Organosulphur Ligands by Inhibition: Trace Determination of Cysteine and Maleonitrilodithiolate [MNDT]. Microchem. J. (Elsevier), 85, 214-221, 2007.
18. R. M. Naik, A. Srivastava, A. K. Verma, S.B.S. Yadav and S. Prasad; The Kinetics and Mechanism of Oxidation of Triethylenetetraaminehexaacetatocobaltate(II) Complex by Periodate Ion in Aqueous Medium. Inorg. React. Mech., (OCP Science, USA) 6, 185-192, 2007.
19. Surendra Prasad and Ram K. Agarwal; Cobalt(II) Complexes of Various Thiosemicarbazones of 4-aminoantipyrine: Syntheses, Spectral, Thermal and Biological Studies. Transition Met. Chem. (Springer Science, UK), 32(2), 143-149, 2007.
20. Ram K. Agarwal and Surendra Prasad; Synthesis, Biological, Spectral and Thermal Properties of Oxovanadium(IV) Complexes of N,N,S-containing Ligands. Revs. Inorg. Chem., (Freund Publishing, London) 26(5), 471-492, 2006.
21. Ram K. Agarwal and Surendra Prasad; Synthesis, Spectral and Thermal Characteristics of Some Ten Coordinated Complexes of Dioxouranium(VI) Derived from Semicarbazones as Primary Ligand and Diphenyl Sulfoxide as Secondary Ligand. Ram. Turkish J. Chem. [Sci. & Technol. Res. Council (STRC), Turkey] 30(5), 553-562, 2006.
22. Ram K. Agarwal, Surendra Prasad, Rajiv Garg and Sushil K. Sidhu; Synthesis and Magneto-Spectral Characteristics of Some Six and Nine Coordinated Complexes of Lanthanides(III) Derived from 4[N-(2’-Hydroxy-1’-Naphthalidene)Amino]Antipyrine-Semicarbazone. Bull. Chem. Soc. Ethiop., 2006, 20(1), 167-172.
23. Surendra Prasad; Kinetic Determination of Mercury(II) at Trace Level from Its Catalytic Effect on a Ligand Substitution Process. J. Anal. Chem. (Springer Link, USA), 60(6), 581-588, 2005.
24. Surendra Prasad; Kinetic Method for Determination of Nanogram Amounts of Copper(II) by Its Catalytic Effect on Hexacynoferrate(III)-Citric Acid Indicator Reaction. Anal. Chim. Acta (Elsevier), 540(1), 173-180, 2005.
25. Surendra Prasad, Radhey M. Naik, Raj K. Tewari, Pradeep K. Singh and Anjani Tewari; The Mercury(II) Catalyzed Ligand Exchange Reaction between Hexacyanoferrate(II) and Pyrazine in Aqueous Medium. Transition Met. Chem. (Springer Science, UK), 30, 968-977, 2005.
26. Ram K. Agarwal and Surendra Prasad; Synthesis, Magneto-Spectral, Biological and Thermal Investigations of Cobalt(II) and Nickel(II) Coordination Compounds of Thiosemicarbazones Derived from 4-Aminoantipyrine. Bioinorg. Chem. Appln., (Freund Publishing, London), 3(3-4), 271-288, 2005.
27. Ram K. Agarwal and Surendra Prasad; Synthesis and Spectral Investigations of Some Platinum Metals Ions Coordination Compounds of 4[N-(Furan-2-carboxalidene)Amino]Antipyrine Thiosemicarbazone and 4[N-(3’,4’,5’-Trimethoxy-benzalidene)Amino]Antipyrine Thiosemicarbazone. Turkish J. Chem. (STRC Turkey), 29, 289-297, 2005.
28. Ram K. Agarwal and Surendra Prasad; Synthesis, Spectral and Thermal Investigation of Some Mixed Ligand Complexes of Thorium(IV) Derived from Semicarbazones and Diphenyl Sulfide. J. Iranian Chem. Soc., 2(2), 168 –175, 2005.
29. Ram K. Agarwal, Surendra Prasad and Neetu Goel; Synthesis Magneto-Spectral and Thermal Characteristics of Some 7-Coordinated Compounds of Lanthanides(III) Chlorides with 4[(Furan-2-ylmethylene)amino]-1,5-dimethyl-2-phenylpyrazol-3-one and Isonicotinic acid (3’,4’,5’-trimethoxy-benzylidene)hydrazide. Turkish J. Chem. (STRC Turkey), 28, 405-413, 2004.
30. Ram K. Agarwal, Surendra Prasad and Neetu Gahlot; Synthesis, Spectral and Thermal Properties of Some Penta-Coordinated Complexes of Oxovanadium(IV) Derived from Thiosemicarbazones of 4-Aminoantipyrine. Turkish J. Chem. (STRC Turkey), 28, 691-701, 2004.
31. Ram K. Agarwal, Surendra Prasad and N.K. Sharma; Synthesis, Spectral and Thermal Properties of Some Mixed Ligand Complexes of Thorium(IV) and Dioxouranium(VI) with Semicarbazones as Primary Ligand and Sulfoxide as Secondary Ligand. Iran. J. Chem. Chem. Eng. (IRDC, Iran), 23(2), 121-133, 2004.
32. Ram K. Agarwal, Surendra Prasad and Indranil Chakraborti; Synthesis and Characterization of Some Lanthanide(III) Chloro Complexes Derived from 4[N-(4’-Hydroxy-3’-Methoxy-benzalidene)Amino]Antipyrine Semicarbazone and 4[N-(3’,4’,5’-Trimethoxybenzalidene)- Amino]Antipyrine Semicarbazone. Iran. J. Chem. Chem. Eng. (IRDC, Iran), 23(2), 113-119, 2004.
33. Surendra Prasad; Catalytic Abstraction of Cyanide in Hexacyanoferrate(II) by Hg2+ in the presence of a-Nitroso b-Naphthol and Trace Determination of Hg(II) by Kinetic Method. Anal. Lett. (Marcel Dekker, USA), 37(13), 2851 – 2867, 2004.
34. Surendra Prasad and Tu’ikolongahau Halafihi; Development and Validation of Catalytic Kinetic Spectrophotometric Method for Determination of Copper(II). Mikrochimica Acta (Springer Link, USA), 142(4), 237-244, 2003.
35. Surendra Prasad; Kinetics and Mechanism of Exchange of Cyanide in Hexacyanoferrate(II) by N-Methylpyrazinium ion in the Presence of Mercury(II) as a Catalyst. Transition Met. Chem. (Kluwer Academic Publishers, UK), 28 (1), 1-8, 2003.
36. Surendra Prasad; Recent Developments in Kinetic Methods for Trace Constituents; Asian J. Chem. (UBS Publishers, India), 15(1), 1-4, 2003.
37. Surendra Prasad and Deepak Kunzru; Spectrophotometric Determination of Phosphorus in Aqueous, Organic Phases Obtained on Pyrolysis of Naphtha. Asian J. Chem. (UBS Publishers, India), 15(2), 930-936, 2003.
38. Surendra Prasad and Tu’ikolongahau Halafihi; Standardization of Kinetic Determination of Nitrite Based on its Catalytic Effect on an Indicator Reaction; Int. J. Envtl. Studies (IAIR, USA), 5, 1-12, 2002.
39. Surendra Prasad; Development and Validation of a Catalytic Spectrophotometric Method for Trace Determination of Ruthenium(III); Asian J. Chem. (UBS Publishers, India), 14(2), 799- 806, 2002.
40. Rita Kumar, Surendra Prasad, Alka Sharma, Anil Kumar and Archana Kapoor; Application of Immobilized Mixed Bacterial Culture for the Degradation of Phenol Present in an Oil Refinery Effluent. J. Environ Sci. Health (Marcel Dekker, USA), A33(6), 1009-1021, 1998.
41. Rajendra Prasad, Surendra Prasad and U.C. Agrwala; Synthesis of Maleonitriledithiolate and Dibenzyldithiomaleonitrile Bridged Ruthenium Complexes Possesing (bipy)2Ru(II) and Cp(EPh3)2Ru(II) Moieties (E = P, As and Sb). Synth. React. Inorg. Met.-Org. Chem. (Marcel Dekker, USA), 25, 1493-1506, 1995.
42. Pradip Das, Surendra Prasad and Deepak Kunzru; Organophosphorus Compounds as Coke Inhibitor During Naphtha Pyrolysis. Effect of Benzyl Diethyl Phosphite and Triphenylphosphine Sulphide. Ind. Eng. Chem. Res. (Am. Chem. Soc., USA), 31, 2251-2255, 1992.
43. Surendra Prasad, P. C. Nigam and Madhu Phull; Study of Mechanistic Features of Tetrahedral-Octahedral Interconversion of Tetracyanozincate(II) to bis(4-(2-Pyridylazo)resorcinol)-zincate(II) by Stopped Flow Technique. Int. J. Chem. Kinetics (John Wiley & Sons, USA), 24, 239-253, 1992.
44. S. Prasad and P. C. Nigam; Kinetic Methods for Trace Analysis Based on Uncatalysed Ligand Substitution Reactions. Chem. Environ. Res. (India Publishers Ltd), 1, 13-21, 1992.
45. Surendra Prasad, R. M. Naik and P. C. Nigam; Kinetics and Mechanism of Ligand Exchange Reactions: A Review. J. Indian Chem. Soc. (Indian Chem. Soc.), 69, 475-480, 1992.
46. Surendra Prasad and Prem. C. Nigam; Catalytic Kinetic Determination of Ultratrace Amount of Ruthenium(III) based on the Oxidation of Benzylamine by Alkaline Hexacyanoferrate(III). Talanta (Pergaman Press, USA), 38, 627-630, 1991.
47. Hari C. Bajaj, Surendra Prasad, Prem C. Nigam and Radhey M. Naik; Kinetics and Mechanism of Ligand Substitution of Mono(Polyen)Nickel(II) Complexes with 4-(2-Pyridylazo)resorcinol. Transition Met. Chem. (Chapman & Hall, UK), 16, 511-517, 1991.
48. Surendra Prasad, Prem C. Nigam and Radhey M. Naik; An Independent Kinetic and Mechanistic Study of the Secondary Reactions in the Substitution of [FeL(OH)] (L=Triethylenetetraaminehexaaceticacid) by Cyanide ions. Trasition Met. Chem. (Chapman & Hall, UK), 15, 58-62, 1990.
49. Pratima K. Mishra, Surendra Prasad and P. C. Nigam; Kinetics and Mechaism of Reaction between Aminopolycarboxylato-manganate(III) Complexes and Cyanide ions: A Reinvestigation of the MnCyDTA-CN Reaction. Tansition Met. Chem. (Chapman & Hall, UK), 15, 429-433, 1990.
50. Surendra Prasad and Prem. C. Nigam; Mercury Catalysed Exchange Reaction of Hexacyanoferrate(II) and Its Application in Trace Element Determination in Environmental Pollution. Indian J. Environ. Protection (Kalpana Corpn., India), 9, 113-117, 1989.
51. P. C. Nigam and S. Prasad; Recent Advances in Trace Determination of Phosgene: A Review. Indian J. Environ. Hlth. (NEERI/CSIR, India