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S. P. Rath
PhD (IACS, Kolkata)
Professor, Department of Chemistry
Research Interest
Unfolding Mystery of Multi-Heme Cytochromes Multiheme cytochromes, that are recognizably different from the monoheme cytochromes, constitute a widespread class of proteins with essential functions in electron transfer and enzymatic catalysis. However, the structural and functional significance of such arrangements is not yet understood. Understanding the significance of these heme structural motifs is crucial for the elucidation of the highly optimized properties of multiheme cytochromes which we are currently engaged in.
Modeling Di-heme Cytochromes: Effect of Inter-macrocyclic Interactions The diheme cytochrome c (DHC2) from G. sulfurreducens is, however, the simplest member of Multiheme cytochromes family, with two heme groups attached through a single polypeptide chain that are found to be different. The observed differences in the axial ligand orientations and porphyrin ring deformations between two heme centers in DHC2 have been proposed to be the consequences of heme-heme interactions which will be explored in details.
Probing Molecular Chirality using Metallo-Bisporphyrin Hosts Supramolecular chirogenesis is one of the most important interdisciplinary field to be looked into, because of its occurrences in many natural (DNA double helix, heme proteins, secondary α-helix structure of proteins etc.) and artificial systems. Exciton Coupled Circular Dichroism (ECCD) is a nonempirical spectroscopic method that is based on detecting the through-space exciton interaction between helically orientated independently conjugated chromophores. Our group is currently engaged in investigating the various aspects of chirality induction and control for probing molecular chirality using Exciton Coupled Circular Dichroism (ECCD).
Light-induced Electron/Energy Transfer The photosynthetic reaction center proteins from Rhodopseudomonas viridis and Rhodobacter spheroides have been isolated in pure form and structurally characterized with X-ray crystallography. The heart of the photosynthetic reaction centre is a pair of chlorophyll molecules, often referred to as the 'special pair'. One of the problems to be solved is the role of pair of chlorophylls, which are placed face-to-face in green plants and photosynthetic bacteria.
CL-205C ,
Department of Chemistry
IIT Kanpur,
Kanpur 208016
Specialization
Bio‐inorganic Chemistry
Education
PhD (1999), IACS, KolkataThesis Supervisor:Prof. Animesh Chakravorty
M.Sc., (Specialization in Inorganic Chemistry): Calcutta University (1994)
B.Sc., (Honors in Chemistry): Calcutta University (1992)
Teaching Area
Primary teaching area:
Inorganic Chemistry
Current Teaching
Inorganic Chemistry
Coordination Chemistry
Bio-inorganic Chemistry
Crystal and Molecular Structure Determination
Applications of Modern Instrumental Methods
Professional Affiliations
Life member, Chemical Research Society of India (CRSI)
Member, American Chemical Society (ACS)
Member, Society for Biological Inorganic Chemistry (SBIC)
Member, Society of Porphyrins and Phthalocyanines (SPP)
Life member, Indian Association for the Cultivation of Science (IACS)
Selected Publications
Efficient Complexation of Pyrrole-bridged Di-Zinc(II) Bisporphyrin with Fluorescent Probe Pyrene: Synthesis, Structure, and Photoinduced Singlet-Singlet Energy Transfer A. Chaudhary and S. P. Rath* Chem. Eur. J., 2011, 17, 11478-11487.
Encapsulation of TCNQ and Acridinium Ion within Bisporphyrin Cavity: Synthesis, Structure, Photophysical and HOMO-LUMO Gap Mediated Electron Transfer Properties A. Chaudhary and S. P. Rath* Chem. Eur. J. 2012, 54, 18, 7404-7417. <
Protonation of an oxo-Bridged Diiron Unit Makes Two Iron Centers Different: A New Class of Diiron(III)-μ-hydroxo Bisporphyrin and Control of Spins by Counter Anions S. Bhowmik, S. K. Ghosh and S. P. Rath* Chem. Eur. J. 2012, 55, 18, 13025-13037.
Effect of Heme-Heme Interactions and Modulation of Metal Spins by Counter Anions in a Series of Diiron(III)-μ-hydroxo Bisporphyrins: Unusual Stabilization of Two Different Spins in a Single Molecular Framework S. K. Ghosh, S. Bhowmik and S. P. Rath* Chem. Eur. J. 2013, 19, 17846-17859.
Unusual Stabilization of an Intermediate Spin of Iron upon Axial Phenoxide Coordination on a Diiron(III)bisporphyrin: Effect of Heme-Heme Interactions S. Bhowmik, S. Dey and S. P. Rath* Chem. Eur. J. 2013, 19, 13732-13744.
Cyclic Zn(II)bisporphyrin Based Molecular Switch: Supramolecular Control of Complexation Mediated Conformational Switching and Photoinduced Electron Transfer P. Mondal and S. P. Rath* Chem. Eur. J. 2016, 22, 5607-5619.
Diiron(III)-μ-Fluoro Bisporphyrins: Effect of Bridging Ligand on the Metal Spin State D. Sil, A. Kumar and S. P. Rath* Chem. Eur. J. 2016, 22, 11214-11223.
Effect of Inter-porphyrin Distance on Spin-state in Diiron(III) μ-Hydroxo Bisporphyrins D. Sil, F. S. T. Khan and S. P. Rath* Chem. Eur. J. 2016, 22, 14585-14597.
Remarkable Anion Dependent Spin state Switching in Diiron(III)-μ-Hydroxo Bisporphyrins: What role do Counter ions play? F. S. T. Khan, A. K. Pandey and S. P. Rath* Chem. Eur. J. 2016, 22, 16124-16137.
Cyclic Bisporphyrin Based Flexible Molecular Containers: Controlling Guest Arrangements and Supramolecular Catalysis by Tuning Cavity Size P. Mondal, S. Sarkar and S. P. Rath* Chem. Eur. J. 2017, 23, 7093-7103.
Probing Bis-FeIV MauG: Isolation of Highly Reactive Radical Intermediates T. Guchhait, S. Sarkar, Y. A. Pandit and S. P. Rath* Chem. Eur. J. (Communication) 2017, 23, 10270-10275.
Intermacrocyclic Interaction Triggers Facile One-pot Synthesis of a Chlorin-Porphyrin Heterodimer Y. A. Pandit, S. Sanfui and S. P. Rath * Chem. Eur. J. 2017, 23, 13415-13422.
Control of Spins by Ring Deformation in a Diiron(III)bisporphyrin: Reversal of ClO4- and CF3SO3- Ligand Field Strength on the Magnetochemical Series. S. Bhowmik, S. K. Ghosh and S. P. Rath* Chem. Commun. 2011, 47, 4790-4792.
Induction of Supramolecular Chirality in Di-Zinc(II) Bisporphyrin via Tweezer Formation: Synthesis, Structure and Rationalization of Chirality S. Brahma, Sk. A. Ikbal, S. Dey and S. P. Rath* Chem. Commun. 2012, 48, 4070-4072.
Transfer and Control of Molecular Chirality in the 1:2 Host-Guest Supramolecular Complex Consisting of Mg(II) bisporphyrin and Chiral Diols: Effect of H-bonding on Rationalization of Chirality Sk. A. Ikbal, S. Brahma and S. P. Rath* Chem. Commun. 2014, 50, 14037-14040.
Step-wise induction, amplification and inversion of molecular chirality through the coordination of chiral diamines with Zn(II)bisporphyrin Sk. A. Ikbal, S. Brahma and S. P. Rath* Chem. Commun. 2015, 51, 895-898.
Metal-coordination-driven Mixed Ligand Binding in Supramolecular Bisporphyrin Tweezers Sk. A. Ikbal, A. Dhamija and S. P. Rath* Chem. Commun. 2015, 51, 14107-14110.
Controlled generation of highly saddled (porphyrinato) iron(III) iodide, tri-iodide and one-electron oxidized complex D. Sahoo and S. P. Rath* Chem. Commun. 2015, 51, 16790-16793.
An Ethane-bridged Porphyrin Dimer as Model of Di-heme Proteins: Inorganic and Bioinorganic Perspectives and Consequences of Heme-Heme Interactions D. Sil and S. P. Rath * Dalton Trans. 2015, 44, 16195-16211.
Hydroxo-bridged diiron(III) and dimanganese(III) bisporphyrins: modulation of metal spins by counter anions F. S. T. Khan, T. Guchhait, S. Sasmal and S. P. Rath * Dalton Trans. 2017, 46, 1012-1037.
Multiheme Proteins: Effect of Heme-Heme Interactions D. Lai, F. S. T. Khan, and S. P. Rath* Dalton Trans. 2018, 47, 14388-14401.
Oxo- and hydroxo-bridged diiron(III) porphyrin dimers: inorganic and bio-inorganic perspectives and effects of intermacrocyclic interactions T. Guchhait, S. Sasmal, F. S. T. Khan and S. P. Rath * Coord. Chem. Rev. 2017, 337, 112-144.
Oxidation Triggers Extensive Conjugation and Unusual Stabilization of Two Di-heme Dication Diradical Intermediates: Role of Bridging Group for Electronic Communication D. Sil, S. Dey, A. Kumar, S. Bhowmik and S. P. Rath* Chem. Sci. 2016, 7, 1212-1223.
A Remarkably Bent Diiron(III)-μ-Hydroxo Bisporphyrin: Unusual Stabilization of Two Spin States of Iron in a Single Molecular Framework S. K. Ghosh and S. P. Rath* J. Am. Chem. Soc. 2010, 132, 17983-17985.
Hydrogen Bonding Interactions Trigger a Spin-Flip in Iron(III)-Porphyrin Complexes D. Sahoo, M. G. Quesne, S. P. de Visser* and S. P. Rath* Angew. Chem. Int. Ed. 2015, 54, 4796-4800.
A Highly Oxidized Cobalt Porphyrin Dimer: Spin Coupling and Stabilization of the Four-Electron Oxidation Product S. Dey, D. Sil and S. P. Rath* Angew. Chem. Int. Ed. 2016, 55, 996-1000.
Silver(III)···Silver(III) Interaction that Stabilize the syn Form in a Porphyrin Dimer Upon Oxidationt A. K. Singh, F. S. T. Khan and S. P. Rath* Angew. Chem. Int. Ed. 2017, 56, 8849-8854.
A Dimanganese(III) porphyrin dication diradical and its transformation to a μ-hydroxo porphyrin-oxophlorin heterodimer A. Kumar, D. Sil, M. Usman and S. P. Rath* Chem. Commun. 2019, 55, 1588-1591.
Counter Ion Triggers Stabilization of Two Geometrical Isomers of a Ni(II)dication Diradical Porphyrin Dimer: Role of Anion-π Interactions A. K. Pandey. M. Usman and S. P. Rath* Chem. Commun. 2019, 55, 7926-7929.
Through Space Spin Coupling in a Silver(II) Porphyrin Dimer upon Stepwise Oxidations: AgII/AgII, AgII/AgIII and AgIII/AgIII Metallophilic Interactions A. K. Singh, M. Usman, G. Sciortino, E. Garribba and S. P. Rath* Chem. Eur. J. 2019, 25, 10098-10110. Chem. Eur. J. 2019, 25, 10021-10021. Chem. Eur. J. 2019, 25, 10025-10025.
Awards & Fellowships
Elected Fellow of Indian Academy of Sciences, Bangalore, 2020
C. N. R. Rao National Prize in Chemical Sciences,, 2018
J. N. Gupta and M. Gupta Chair Professor, IIT Kanpur (2017-2020)
Elected Fellow of National Academy of Sciences, 2017
Elected Fellow of West Bengal Academy of Science & Technology, 2017
Member, Editorial Board, Chirality, 2019
Member, Editorial Advisory Board, Current Inorganic Chemistry, 2018
Bronze Medal from Chemical Research Society of India (CRSI)- 2015
Alexander von Humboldt Research Fellowship for Experienced Researcher in 2012
P. K. Kelkar Faculty Research Fellowship from IIT Kanpur (2009-2012)
Received Commendations several times from the Director, IIT Kanpur for excellence in teaching as “Outstanding Instructor”
Research Result
Keywords
Inorganic Chemist Bio-inorganic chemist
Professional Experience
Professor, Department of Chemistry,Indian Institute of Technology Kanpur, June 2014 to date
AvH Fellow (Experienced Researcher) (academic host Prof. Dr. Peter Comba)Anorganisch-Chemisches InstituteHeidelberg University, GermanyDec. 2012-to-July, 2013
Associate Professor, Department of ChemistryIndian Institute of Technology Kanpur, May 2009-May 2014
Assistant Professor, Department of ChemistryIndian Institute of Technology Kanpur, Dec. 2004-April 2009
NIH Post-doctoral Research Associate (with Prof. Alan L. Balch)Department of Chemistry, University of California, Davis, USA. 2001-2004
Current Research
Rath's group at IIT Kanpur is engaged studying a wide range of bioinorganic and biological systems, all of which fall under the general theme of gaining a better understanding of the heme centers in heme proteins that are vital to the life of almost all living organisms. The group is currently engaged in several broad research areas such as: Unfolding Mystery of Multi-Heme Cytochromes Multiheme cytochromes c constitutes a widespread class of proteins with essential functions in electron transfer and enzymatic catalysis. Understanding the significance of these motifs is crucial for the elucidation of the highly optimized properties of multiheme cytochromes c. Probing Molecular Chirality using Metallo-Bisporphyrin Hosts with Exciton Coupled Circular Dichroism (ECCD) The relative orientation of two chromophores in space in a chiral host-guest complex results in a bisignate CD curve with two bands of opposite sign and similar intensity in the porphyrin spectral regions which is diagnostic of the guest's absolute configuration. Light Induced Electron/Energy Transfer One of the problems to be solved was the role of 'special pair' in photosynthsis which is being investigated extensively. The Rath's group has been using extensively a wide variety of spectroscopic techniques including X-ray diffraction study, variable temperature magnetic, NMR, EPR and Mössbauer spectroscopy and also DFT for structure-function correlation. The progress of the reactions are monitored in situ in solution along with the structural elucidation utilizing paramagnetic NMR spectroscopic technique.