Time Program

09:00-09:20 Registration

09:20-09:30 Welcome Remarks by HOD

Session 1: Student Chair

09:30-10:00 Prof. Rodney A. Fernandes Protecting-Group-Free Synthesis of Natural Products:

A Step Toward Economy and Efficiency in Synthesis

10:00-11:00 Student Oral Presentation

1 Ritutama Ghosh Biophysical Insights into Formation and Prevention of Amyloid Hydrocolloids:

Implications in Neurodegenerative diseases

2 Sunil Pulletikurti Role of Carbonyl Group at C7 Position of Endo-norbornene Derivatives on

Olefin Metathesis: Synthesis of Polycycles and Heterocycles

3 Vishal Kotha Low-Temperature Synthesis of K-substituted LaMnO3

4 Aarti Sindhu Theoretical Investigation of Electronic Energy Transfer (EET) in the

Photosynthesis Process using Semi-classical Method

5 Parichita Saha A Universal Tetrapeptide Scaffold for Tunable Transmembrane Cation

Transport

6 Archita

Bhattacharjee Meso/Macro Porous Liquid for CO2 Capture, Storage and Catalytic Conversion

7 Asmita Sen Probing the Mechanistic Study of Aliphatic C-H Nitration By SYRB2:

QM/MM Approach

8 Pravas Dolui Ligand Enabled Palladium Catalyzed γ -C(sp3)-H Arylation of Free Carboxylic

Acid

9 Nandini Sharma Allosteric Regulation Mechanism of Purine Biosynthetic Pathway Enzyme

10 Santanu Jana Synthesis of Trehalose Glycolipids

11 Amitrajait Mukherjee Do All Quantum-dots in an Ensemble have the Same

Origins of Photo-blinking?

12 S. Senthilkumar Synthesis and Crystal Structures of Carboxylate and Phosphonate Metal–

Organic Frameworks (MOFs)

11:00-11:15 Group Photo and Tea

11:15-11:50 Poster Session

Session 2: Student Chair

11:50-12:30 Student Oral Presentation

13

Itisha Dwivedi Resistive Random Access Memory Devices by Different Organic–Inorganic

Hybrid Perovskites

14 Geetanjali Sontakke

Rh(II)-Catalyzed Denitrogenative Transannulation of N-Sulfonyl-1,2,3-

triazolyl Cyclohexadienones for the Synthesis of Benzofurans and Cyclopropa[cd]indole-carbaldehydes

15 Vinodhini G A Systems Biology Approach to Understand Effect of Serum Level on

Mammalian Cell Cycle Progression Variability

16 Harish S. Kunchur PdII, and PtII Assisted Tandem P−C Bond Breaking and P−N Bond Formation

Reactions from an Amide Functionalized Bisphosphine: Synthesis,

Mechanistic, and Structural Studies

17 Yuvraj Dangat Exploring the Enantioselectivity of Rh-Yanphos Catalyzed -methyl Styrene

Hydroformylation : Added Insights from Theory

18 Shalini Tripathi Influence of Counter-Anion on the Zero Field Splitting of Tetrahedral Co(II)

Thiourea Complexes

19 Priyanka Deshmukh Synthesis of Methyleugenol and Estargol Induced DNA Damages to Study

Translesion DNA Synthesis

20 Santosh Ranga Excess Electron Interactions with Solvated GC Base Pair: QM/MM Study

12:30-13:00 Prof. Anindya Datta Key factors for design of solid emitters by aggregation of organic

fluorogens.

13:00-14:00 Lunch Time

Session 3:Student Chair

14:00-14:30 Prof. Gopalan Rajaraman Role of Ab initio Calculations in the Design of Transition Metal

Based Single-Ion Magnets

14:30-15:25 Student Oral Presentation

21 Sanyog Kumari Stereoselective Synthesis of Tetrahydrocyclohepta[b]indole Derivatives by

Cascade Radical Cyclization of 3-Propargylated-2-alkenyl indoles

22 Anish Chakraborty A Dressed Coupled Cluster Theory for Molecular Energetics: H-Bonded and

Strongly Correlated Systems

23 Farheen Fatima Khan Redox Assisted Oxidative C-C Cleavage in Diruthenium Complexes of 2,2'-

Pyridil

24 Hemen Gogoi Solvent Mediated Relaxation Dynamics of Core-Shell Au-SiO2 Nanoparticles

25 Prosenjit Isar Facile Synthesis of Fused Core-Modified Sapphyrins

26 Ramalingam Kailasham

Wet and Dry Internal Friction Can be Measured with the Jarzynski Equality

27 Amit Bhowmik Iron(III)/O2-Mediated Regioselective Oxidative Cleavage of 1-Arylbutadienes

to Cinnamaldehydes

28 Pranav Adhyapak Biophysical Insights into the Spatially OrganizedCell Envelope of

Mycobacterium Smegmatis.

29 Ratika Maini Synthesis of Hole Transport Materials Using Pentiptycene Core as the Building

Block

30 Ashiv Narula Carrageenan Beads Incorporated Fluorophoric calix[4]arene Conjugate for Selective, Efficient, Reversible and Fingerprint Detection of Trinitrophenol

31 Sohan Lal Design and Synthesis of Highly Dense Homocubane Derivatives

15:25-16:25 Poster Session

16:25-16:45 High Tea

Session 4: Student Chair

16:45-17:15 Prof. M. S. Balakrishna IYPT 2019 Talk: It is all about the Periodic Table

17:15-18:00 Teaching Awards, Certificate distribution, and Concluding Remarks with Feedback

18:00 Onwards

Cultural Program

Poster Details

Poster No. Student Name Title

1 Amruta Joshi Interaction of proteins and drugs with non- ionic surfactant.

2 Sushil Swaroop

Pathak

Exceptional self-assembly of Ag and Au nanoparticles in

cubic arrangement

3 Chinmay S Pradhan Modelling non-adiabatic and quantum effects near metal

surface

4 Umatai Hale Diketopiperazines as ion transporters and templates for

functionalized membranes

5 Naveen Kumar P M

Investigating the interactions and resultant micro-structure of

protein-polymer surfactant bioconjugates with nematic liquid

crystalline phase

6 Reshma Jose How the spin states control the gas adsorption properties in

Cr-BTT based metal organic frameworks

7 Jyoti Prasad Biswas Co‐ordination assisted distal C−H alkylation of fused

heterocycles

8 Ruchika Bhujbalrao Probingmechanism of ribosomal methyltransferases involved

in antibiotic resistance

9 Kabita Pradhan Studies towards total synthesis of tetrasaccharide repeating

unit of Vibrio cholerae O43

10 Jaladhar Mahato Spatially and spectrally resolved FRET microscopy

11 Tejamani Behera Spatially synchronous fluorescence blinking and flickering of

entire perovskite micro-rods

12 Anuj Kumar Thermally labile layered alkali metal iso-propyl phosphate

13 Ananya Shah Nanostructured carbons for solar thermal conversion for

highly efficient and rapid water evaporation

14 Amitava Giri Unraveling the importance of cell to cell interactions and

underlying fluctuations in neural cell fate decisions

15 Anurag Singh

Palladium-catalyzed highly diastereoslective cascade

dihalogenation of alkyne-tethered cylcohexadienones via

umpolung of palladium enolate

16 Kote Basvaraj Shivaji Phosphine appended with N-heterocycles: Synthesis,

transition metal chemistry and catalytic applications

17 Dipak Fartade

Stereoselective synthesis of medium ring [1,n]-heterocycle-

fused chromenes using 7/8/9-*Endo-Dig* And 7/8-*Exo-

Dig* hydroalkoxylation-formal-[4+2]-cycloaddition cascade

18 Satendra Sahgal Synthesis and biophysical evaluation of G-quadruplex

stabilizing and i-motif destabilizing ligands

19 Divya Tripathi Water mediated electron attachment to nucleobases

20 Mohd Wasim

Importance of transition and lanthanide metal Complexes:

Application in magnetism, catalysis, device fabrication and in

biological system

21 Dashrath Jangid and

Ashvin Gangani

Brønsted Acid-Mediated Reaction in Organic Synthesis:

Synthesis of Coumarin and Butenolide 4-Sulfonates

and 4-Pyranones

22 Fariyad Ali Ultrafast carrier relaxation dynamics of Cu doped

CdSenanotetrapods

23 Mohd Asif Ansari

Di, Tri and Tertanuclear Ruthenium Complexes of a

Heterocyclic and Quinonoid Bridging Ligand: Valence and

Spin Alternatives for the Metal/Ligand/Metal Arrangement,

Non-Innocence and Mixed Valency

24 Avisikta Sinha Synthesis and studies of dibenzothiophene/ dibenzofuran

embedded expanded macrocycles

25 Ligesh T Dynamics of a self-propelled janus particle in a sea of

polymers

26 Jyoti Agawane Process intensification through continuous flow

27 Aswin Srivatsav T Dynamical organisation of compositionally distinct inner and

outer membrane lipids of Mycobacteria

28 Sirilata Polepalli Synthesisand applications of new protein- Inorganic hybrid

materials

29 Chenikkayala

Sivasankara

One-pot construction of functionalized

spirodihydronaphthoquinone-oxindoles via Hauser-Kraus

annulation of sulfonylphthalide with 3-alkylideneoxindoles

30 Shreyata Dey

Stereodirecting Mesoioninc Singlet Carbene Complexes:

Synthesis and Application in Asymmetric Catalysis

31 Priyanka Sakhare

Copper catalyzed oxidative C−C bond cleavage of 1,2-

Diketones: A direct route to 1,8 Naphthalimides, Biphenyl-

2,2’-Dicarboxamides and N-Heterocyclic amides

Faculty Oral Talks Abstracts

Protecting-Group-Free Synthesis of Natural Products:

A Step Toward Economy and Efficiency in Synthesis

Rodney A. Fernandes*

rfernand@chem.iitb.ac.in

Department of Chemistry, Indian Institute of Technology Bombay, Mumbai, Maharashtra, India

Protecting-group-free (PGF) synthesis enables step economy and increases the efficiency of

synthesis.1 Our research in the synthesis of many natural products designing PGF based strategies

have resulted in shorter sequences than that known in the literature. The stereoselective total synthesis

of the following listed natural products2-6 will be discussed.

References:

1. Protecting-Group-Free Organic Synthesis: Improving Economy and Efficiency, Fernandes,

R. A. Ed. John-Wiley & Sons, 2018.

2. (a) Fernandes, R. A.; Kattanguru, P. J. Org. Chem. 2012, 77, 9357. (b) Fernandes, R. A.;

Kattanguru, P. Asian J. Org. Chem. 2013, 2, 74. (c) Chaudhari, D. A.; Kattanguru, P.;

Fernandes, R. A. RSC Adv. 2015, 5, 42131.

3. Kunkalkar, R. A.; Laha, D.; Fernandes, R. A. Org. Biomol. Chem. 2016, 14, 9072.

4. Nallasivam, J. L.; Fernandes, R. A. Org. Biomol. Chem. 2017, 15, 708.

5. (a) Ramakrishna, G. V.; Fernandes, R. A. Org. Lett. 2019, 21, 5827. (b) Ramakrishna, G. V.;

Fernandes, R. A. J. Org. Chem. 2019, DOI: 10.1021/acs.joc.9b02461.

6. Kunkalkar, R. A.; Fernandes, R. A. J. Org. Chem. 2019, DOI:10.1021/acs.joc.9b01952.

Key factors for design of solid emitters by aggregation of organic fluorogens

Tuhin Khan, Souradip Dasgupta and Anindya Datta

Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400 076, India

Email: anindya@chem.iitb.ac.in

Aggregation induced enhancement of emission (AIEE) of fluorogenic molecules been studied using

steady state and time resolved spectroscopy, starting with salophen, a fluorogenic Schiff base.

Fluorescence quantum yield and lifetime of salophen increase by orders of magnitude upon

complexation and in solid form/ matrix. The extent of enhancement is significantly more in its

monomeric Al3+ complex (SalAl+) than in its dimeric Zn2+ complex (SalZn).1 Interestingly,

fluorescence is quenched in the SalAl+ crystals. These trends are rationalized in the light of molecular

arrangement of salophen and its complexes in their pure solid forms.2 Introduction of alkoxy groups

in salophen ring is found to alter not only the photophysics, but also molecular packing of the

molecules in their crystals, leading to a higher emissivity of the Al3+ complexes in their crystalline

form.3 More recently, we have studied other Schiff bases, in which Zn complexes are dimeric, but the

ligand molecules are not stacked. These complexes turn out to be significantly more emissive than

the free ligand, thereby supporting the role of p-stacking in determining the emissivity of these

complexes. Careful selection of structural and electronic properties is required to optimize emissivity

of similar complexes and free ligands in their solid state.4

References

(1) Khan, T.; Vaidya, S.; Mhatre, D. S.; Datta, A. The Prospect of Salophen in Fluorescence

Lifetime Sensing of Al3+. J. Phys. Chem. B 2016, 120 (39), 10319–10326.

(2) Khan, T.; Datta, A. Impact of Molecular Arrangement and Torsional Motion on the

Fluorescence of Salophen and Its Metal Complexes. J. Phys. Chem. C 2017, 121 (4), 2410–

2417.

(3) Khan, T.; Datta, A. Enhanced Fluorescence with Nanosecond Dynamics in the Solid State of

Metal Ion Complexes of Alkoxy Salophens. Phys. Chem. Chem. Phys. 2017, 19 (44), 30120–

30127.

(4) Dasgupta, S.; Khan, T.; Datta, A. Excited State Dynamics of Fluorogenic Molecules,

in Advances in Spectroscopy: Molecules to Materials, Singh, D. K.; Das, S.; Materny, A. eds.

Springer 2019

Role of Ab initio Calculations in the Design of Transition Metal Based Single-Ion

Magnets

Gopalan Rajaraman

Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai.

Email: rajaraman@chem.iitb.ac.in

Molecular magnetism is one of the vastly growing research fields with an aim to design the molecules

and materials with tunable magnetic and electronic properties.Error! Reference source not found.

Their synthesis, characterization and implementation as devices which creates lively crossroad among

chemistry, physics and material science: a multidisciplinary research field. These molecules have wide

spread potential applications ranging from magnetic storage devices, spintronics, Q-bits in quantum

computing to magnetic coolants.Error! Reference source not found. Single-molecule magnets

(SMMs) are the molecules which show slow relaxation of magnetization below the critical

temperature and exhibit hysteresis loop similar to classical magnets. SMMs offer key advantage over

classical magnets due to their light weight, solubility and multifunctional behaviour. Theoretical tools

are indispensable in this arena2 for understanding the observed magnetic properties. The strength of

these methods is not only limited rationalization but also to predict novel molecules which can exhibit

superior magnetic properties. In this presentation, I will research effort undertaken in our group

towards achieving this goal.2

References:

1. R. Sessoli, D. Gatteschi, A. Caneschi, M. A. Novak, Nature, 1993, 365, 141.

2. Singh S. K. and Rajaraman, G. Nature Commun. 2016 7:10669, Gupta,S.K.; Rajeshkumar,T.;

Rajaraman,G. and Murugavel,R. Chem. Sci., 2016,7, 5181-5191; Singh,M.K.;Yadav,N.;

Rajaraman,G. Chem. Commun. 2015,51, 17732-17735. T. Gupta, G. Rajaraman Chem.

Comm., 2016, 52, 8972.

3. Rajaraman and Murrie and co-workers, Chem. Sci., 2018, 1551; Chem. Sci., 2019, 6354.

Rajaraman and co-workers, Chem. Eur. J., 2019, DOI: 10.1002/chem.201903618.

It is all about the Periodic Table

M S Balakrishna

krishna@chem.iitb.ac.in

Department of Chemistry, Indian Institute of Technology Bombay,

Powai, Mumbai 400076

UNESCO has designated 2019 as the International Year of the Periodic Table to mark 150th

anniversary of the Mendeleev periodic table. Periodic table is a symbol of learning and an iconic

image of science. It is an essential and a complete tool to understand science in all aspects including

day-to-day life. The present periodic table with 118 elements, all known and named, includes 94

natural and 24 man (woman) made elements.

Mendeleev published his periodic table, popularly known as Mendeleev Periodic Table, in 1869, in

which all known elements have been arranged in increasing order of their atomic weight with a

statement: “The properties of the elements are a periodic function of their atomic weight”. Before

Mendeleev proposed his periodic table many researchers and chemists made attempts to arrange the

known elements in an order along with their atomic weights, and other physical and chemical

properties. Among them the prominent ones being: Lavoisier, Berzelius, Dobereiner, Newlands and

Meyer. Later Ramsay and physicist Releigh discovered all inert gases, and trans-uranium elements

by Seaborg, Oganessian, Ghiorso and others. The talk includes brief discussion on historic

developments along with the fascinating stories about the discovery of a few elements.

Student Oral Talks Abstracts

Biophysical Insights into Formation and Prevention of Amyloid Hydrocolloids:

Implications in Neurodegenerative diseases

Ritutama Ghosh and Nand Kishore

Abstract: Aggregation and disorder in proteins is associated with neurodegenerative disorders such

as, Alzheimer’s, Parkinson’s, Huntington’s and prion diseases.1 Accumulation of protein fibrils leads

to amyloidosis, though recently their catalytic properties are also being explored in combination with

metals. Cross-β sheet quaternary structures are adopted by the amyloids. The effect of anticancer

drugs on fibrillation/aggregation properties of the transport protein bovine serum albumin has been

studied to understand how molecules act as inhibitors in the process of aggregation. The process of

fibrillation/aggregation was monitored by thioflavin T assay, 8-Anilino-1-naphthalenesulfonic acid

assay, transmission electron microscopy and dynamic light scattering. The energetics of interactions

of the potential inhibitors has been studied with the protein at various stages of fibrillation by

isothermal titration calorimetry. The extent of structure/conformation induced by the inhibitors has

been studied by differential scanning calorimetry along with circular dichroism spectroscopy. It is

observed that anticancer drugs altretamine, 5-fluorouracil and hydroxyurea, act as inhibitors of

fibrillation in serum albumin and therefore can also be useful in treating the neurodegenerative

diseases. The thermodynamic signatures of the drugs with the protein thus obtained at native,

nucleation/elongation and matured stages of the fibrillation/aggregation have enabled an

understanding of mechanistic details of prevention of fibrils, identification of the functional groups

responsible for inhibition and hence establishing structure-property-energetics relationships.

Reference:

1. Chatani, E., and Yamamoto, N. 2018. Recent progress on understanding the mechanisms of

amyloid nucleation. Biophys. Rev., 10, 527-534.

Role of carbonyl group at C7 position of endo-norbornene derivatives on olefin

metathesis: Synthesis of polycycles and heterocycles

Sunil Pulletikurti, Kotha Sambasivarao*

Abstract: Role of carbonyl group at C7 position of endo-norbornene derivatives on olefin metathesis

was not studied. Here, we demonstrated that the presence of carbonyl group at C7 position is

preventing to undergo metathesis of olefin of endo-norbornene derivatives due to complexation

between metal alkylidene and olefin of endo-norbornene derivatives via DFT studies, time-dependant

NMR studies and ESI-MS analysis. DFT studies depicts that the orientation of metal alkylidene is

near perpendicular to that of norbornene olefin. Time-dependent NMR studies showed the presence

of a new proton signal in the metal alkylidene region, which indicates the formation of metal complex

with carbonyl group of substrate. These observation were further proved by ESI-MS analysis (Figure

1a). Later these endo-keto norbornene derivatives were reduced to hydroxyl derivatives which gives

us the [6/5/6] carbo-tricyclic, [6/5/6] oxa-tricyclic derivatives and [5/6/5] carbo-tricyclic derivatives

of a class of natural products on ring-rearrangement metathesis (Figure 1b).

References

1. Sanford, M. C., Love, J. A., Grubbs, R. H. J. Am. Chem. Soc. 2001, 123, 6543.

2. Eaton, P. E., Sidhu, R. S., Langford, G. E., Cullison, D. A., Pietruszewski, C. L. Tetrahedron

1981, 37, 4479.

3. Kotha, S., Pulletikurti, S. RSC Adv. 2018, 8, 14906.

Low-Temperature Synthesis of K-substituted LaMnO3

Vishal Kotha and Leela Srinivas Panchakarla*

Abstract: LaMnO3 (LMO) is an antiferromagnetic insulator, but the substitution of La3+ by alkaline

earth metals makes it ferromagnetic metallic system. Doping of the La site in LMO by divalent

cations (e.g., Ba2+, Sr2+, and Ca2+) is known for the last five decades. In these manganites, unique

phenomena like charge, spin, and orbital ordering take place. However, recently, the discovery of

colossal magnetoresistance (CMR) in these doped LMO has triggered the attention of the scientific

community. The limitation of not knowing to synthesize in controlled morphology mainly in one-

dimensional is a challenge to apply in the advanced technologies. We have approached via solution-

based synthesis, i.e., the hydrothermal method where one can have reasonable control over the size

and morphology of the compound. For the first time, our studies made us understand the crystal

growth mechanism, which is quite different from the classical nucleation and growth mechanism

followed by the tri-component nucleation.

Reference:

1. Shivkumara C. Subraya M. Solid state Sci. 2001,3,43

2. Markovich, V.; Jung, G.; Fita, I.; Mogilyansky, D.; Wu, X.; Wisniewski, A.; Puzniak, R.;

Froumin, N.; Titelman, L.; Vradman, L.; Herskowitz, M.; Gorodetsky, G. J. Phys. D. Appl.

Phys. 2008, 41, 185001

3. Kuepper, K.; Falub, M. C.; Prince, K. C.; Galakhov, V. R.; Troyanchuk, I. O.; Chiuzbaian, S.

G.; Matteucci, M.; Wett, D.; Szargan, R.; Ovechkina, N. A.; Mukovskii, Y. M.; Neumann, M.

J. Phys. Chem. B 2005, 109, 9354.

4. Wang, X. R.; Li, C. J.; Lü, W. M.; Paudel, T. R.; Leusink, D. P.; Hoek, M.; Poccia, N.;

Vailionis, A.; Venkatesan, T.; Coey, J. M. D.; Tsymbal, E. Y.; Ariando; Hilgenkamp, H.

Science 2015, 349, 6249.

5. Shivakumara, C.; Bellakki, M. B. Bull. Mater. Sci 2009, 32, 443

Theoretical Investigation of Electronic Energy Transfer (EET) in the

Photosynthesis Process Using Semi-classical Method

Aarti Sindhu and Amber Jain

Abstract: The process of photosynthesis has a remarkable efficiency in the energy transfer from the

absorbance site to reaction centre of the system. In a recent spectroscopic experiment (Engal GS, et

al. (2007), Nature 446, 782-786), on Fenna–Mathews-Olsan (FMO) complex, the wavelike transfer

of energy from one site to another have been observed for half of a picosecond time at cryogenic

temperature and these quantum beatings were considered to be responsible for the efficient and robust

energy transfer in the photosynthesis. Further, there have been several theoretical attempts to simulate

the system and extract out the roots of these observed quantum beatings, and to find whether these

are really related to the efficiency or robustness of the process. In the present work, we used semi-

classical method (Surface Hopping) to simulate the FMO system using a model Hamiltonian and

compare the results with the exact numerical method (Hierarchical Equation of motion (HEOM)) that

have been done previously on the same system. We have been working on the system to target

multiple aims. The most important among is to draw out the significance of Nuclear Quantum Effects

(NQE) which is the advantage of using semi-classical method over exact HEOM. And it is found that

for some pairs of FMO sites, NQE plays an important role.

A Universal Tetrapeptide Scaffold for Tunable Transmembrane Cation

Transport

Parichita Saha and Dr. Nandita Madhavan*

Abstract: Ion transporters play important role in maintaining the physiological activities in organic

systems. Natural ion transporters regulate the entry and exit of ions across cell membrane and thus

maintain the proper concentration of important ions in the body fluids.1 The importance of the

synthetic ion transporters and receptors lie in the fact that they help in understanding the features and

functions of their otherwise unstable natural counterparts.2 Herein we explore the relationship

between ion selectivity and scaffold design in peptide templates.3 We report a small tetrapeptide

scaffold for cation transport. The selectivity of the designed peptides has been tuned by varying the

aromatic units incorporated in the tetrapeptide template. Pybox incorporated tetrapeptides were found

to transport Cu(II) while calcium transport was achieved with scaffolds containing both triazole and

pyridine units (Figure 1).4

Figure: Tuning ion selectivity based on aromatic units present in peptide scaffolds

References:

1. B. Hille, Ion Channels of Excitable Membranes, 3rd ed., 2001.

2. E. Gouaux and R. MacKinnon; Science., 2005, 310, 1461-1465.

3. D. Basak, P. Saha and N. Madhavan, ChemistrySelect., 2018, 33, 9731-9735.

4. P. Saha and N. Madhavan, unpublished results.

Meso/Macro Porous Liquid for CO2 Capture, Storage and Catalytic Conversion

Archita Bhattacharjee, and Kamendra P.Sharma*

Abstract: Permanent pores combined with fluidity renders new properties to porous liquids

otherwise not seen in porous solids. In my talk I will show the design and development of a new class

of water-less porous liquid comprising a mixture of polymer-surfactant modified hollow silica

nanorods and carbonic anhydrase enzyme. The composite mixture having a melting point transition

at ~ 20 °C, can be used to sequester/adsorb gaseous CO2 (5.5 cc/g) at 273K and 1 atm pressure.

Further, we show using a combination of turbiditimetry, optical and electron microscopy experiments

that, carbonic anhydrase, can convert the slowly releasing carbon dioxide into carbonate ion. This

reaction can be monitored by the formation of CaCO3 crystals formed due to reaction of carbonate

ion and pre-dissolved CaCl2 salt (68μM) in the composite liquid. The growth of calcite and aragonite

crystals (as observed from XRD) over 48 hrs leads to ~75% decrease in the transmittance after

sequestration of CO2. Moreover, we show CO2 storage capabilities of the water-less composite

porous liquid by trapping the gas within the hollow silica nanorods at -60 °C i.e. below the glass

transition temperature of the system.

References:

1. Zhang, J., Chai, S.H., Qiao, Z.A., Mahurin, S.M., Chen, J., Fang, Y., Wan, S., Nelson, K., Zhang,

P. and Dai, S., Angew. Chem. Int. Ed., 2015, 54, 932-936. 2. Jo, B.H., Seo, J.H., Yang, Y.J., Baek, K., Choi, Y.S., Pack, S.P., Oh, S.H. and Cha, H.J., ACS

Catal., 2014, 4, 4332-4340.

Probing the Mechanistic Study of Aliphatic C-H Nitration by SYRB2: QM/MM

Approach

Asmita Sen, Gopalan Rajaraman*

Abstract: Syringomycin biosynthesis enzyme 2 (SyrB2) belongs to the αKG-dependent halogenase

family. It is found to chlorinate the γ-carbon of L-threonine in the biosynthesis of a phytotoxin called

syringomycin E. Recently, Bollinger et al.1 showed that wild type halogenase SyrB2 also found to

be able to perform C−N bond formation reactions by substituting the native halide ion with the

nitrogenous anions N3 − and NO2 − . These results hint that the Cl is not by itself the cause of the

selectivity of halogenation over hydroxylation, and they thereby underscore the need to understand

why, unlike other similar enzymes, C−H activation does not end with hydroxylation. In this study,

we have focused on the mechanistic aspect of the aliphatic nitration of the L-threonine substrate by

the SyrB2 protein. I have studied small model (with active site only), large model (active site along

with the surrounding amino acid residues that involve with the active site via hydrogen bonding) and

QM/MM study with the entire protein matrix. Calculation on the realistic system i.e. QM/MM

calculation shows that nitrated product is formed exclusively. Our Small model calculations reveal

that there is a competitive nitration with hydroxylation although nitration is favored over

hydroxylation. With large model, the selectivity increases and the result resembles with the QM/MM

results. Based on these calculations we concluded that, we can continue our study with large model

and we have the comparative study with varying substrate and found that HAA step is the rate limiting

one and the reactivity is Aba-S-SyrB1> Thr- S-SyrB1 > Nva-S-SyrB1. We have explored the

reactivity in presence of external oriented electric field.

Reference:

1. Matthews, M. L.; Chang, W.-c.; Layne, A. P.; Miles, L. A.; Krebs, C.; Bollinger Jr, J. M. Nat

Chem Biol2014, 10, 209-215.

H2O

His235

Cl

His116

Ligand Enabled Palladium Catalyzed γ-C(sp3)-H Arylation of Free Carboxylic

Acid

Pravas Dolui, Debabrata Maiti*

Abstract: C-H functionalization of aliphatic carboxylic acids without attaching exogenous auxiliary

has been so far limited at the proximal γ-position1. Herein, we demonstrate a ligand enabled

palladium catalyzed first regioselective distal γ-C(sp3), γH functionalization of aliphatic carboxylic

acids without incorporating an exogenous directing group2. Aryl iodides containing versatile

functional groups including complex organic molecules underwent the γ-C(sp3) γH arylation reaction

with good to excellent yields. Interestingly, weak coordination of carboxylate group can be further

extended for sequential hetero di-arylation.

Reference:

2. Zhu, Y., Chen, X., Yuan, C., Li, G., Zhang, J., Zhao, Y. Nat. Commun. 2017, 8, 14904.

3. Dolui, P., Das, J., Chandrashekar, H. B., Anjana, S. S., Maiti, D. Angew. Chem. Int. Ed.

2019,

Allosteric Regulation Mechanism of Purine Biosynthetic Pathway Enzyme

Nandini Sharma1, Padmani Sandhu1, Navjeet Ahalawat2, Jagannath Mondal2 and Ruchi Anand1,*

Abstract: Formylglycinamidine (FGAM) synthetase, a bi-functional enzyme from purine

biosynthetic pathway has been studied for the investigation of allosteric regulation controlled by a

long flexible loop present approximately ~30Å apart from the catalytic site. FGAM synthetase from

Salmonella typhimurium encoded by purL gene (StPurL) is a single polypeptide of 143 kDa size,

composed of glutaminase, FGAM synthetase, N- terminal and a linker domain [1]. Glutamine

hydrolysis occurs in the glutaminase domain releasing ammonia which is further migrated towards

the FGAM domain via a ~25Å long hydrophobic tunnel where FGAR

(formylglycinamideribonucleotide) to FGAM (formylglycinamidineribonucleotide) conversion

happens [1]. The FGAR binding site is hypothesized to be capped by a long flexible disordered loop

during the course of reaction. Employing a combination of biochemical and X-ray crystallographic

studies, we show that long distance communication, between distal active sites, is initiated by an

allosteric switch that resides in a this conserved catalytic-loop. Further, molecular dynamics

simulations help to delineate the transient states that bring out central role of non-functional N-

terminal domains. We show that carefully orchestrated conformational changes, facilitated by an

interplay of dynamic interactions at the allosteric switch and adaptor-domain interface control

reactivity as well as concomitant formation of the ammonia tunnel. The study asserts that substrate-

channeling is modulated by allosteric hot-spots that alter protein energy landscape thereby, allowing

it to adopt transient conformations paramount for function.

Reference:

1. R.Anand, A. A.Hoskins, J.Stubbe & S. E.Ealick (2004) Domain Organization of Salmonella

typhimurium Formylglycinamide Ribonucleotide Amidotransferase Revealed by X-ray

Crystallography. Biochemistry 43 (32), 10328-10342.

Synthesis of Trehalose Glycolipids

Santanu Jana, Vikram A. Sarpe and Suvarn S. Kulkarni*

Abstract: M. tuberculosis sulfolipids SL-1, Ac2SGL and SL-3 are highly immunogenic and potential

vaccine candidates.1 In the course of our studies directed towards synthesis of trehalose

glycoconjugates,2 We established a novel methodology for the regioselective O6 acylation of the 2,3-

diacyl trehaloses. The methodology was employed to access M. tuberculosis sulfolipid SL-3, related

triester glycolipid analogues, and to achieve the first total synthesis of the tetraacylated trehalolipid

from M. paraffinicum.3 These glycolipids are potential candidates for serodiagnosis and vaccine

development for tuberculosis.

Another class of fungal glycolipids emmyguyacins A and B inhibit the pH dependent conformational

change of hemaglutinin A during replication of the Influenza virus.4 Structurally, compound 1 has a

gluco-galacto trehalose core and 2 is a gluco-gluco diastereomer (Figure 1). Both glycolipids contain

a novel acid chain at the 3-position, 17-oxalyloxydocosanoic acid. Our efficient route, which involves

regioselective functionalization of trehalose and the synthesis of R and S enantiomerically pure side

chain starting from one chiral synthon S-epichlorohydrin, allows rapid access to adequate amounts of

chemically pure emmyguyacin analogues including the desoxylate derivatives for SAR studies.5

References:

2. Goren, M. B. Biochim. Biophys. Acta. 1970, 120, 116-126.

3. Sarpe, V. A.; Kulkarni, S. S. Org. Lett. 2014, 16, 5732-5735.

4. Sarpe, V. A.; Jana, S.; Kulkarni, S. S. Org. Lett. 2016,18, 76-79.

5. Boros, C.; Katz, B.; Mitchell, S.; Pearce, C.; Swinbank, K.; Taylor, D. J. Nat. Prod. 2002, 65,

108–114.

6. Jana, S.; Sarpe, V. A.; Kulkarni, S. S. Org. Lett. 2018, 20, 6938–6942.

Do All Quantum-Dots in an Ensemble have the Same Origins of Photo-blinking?

Amitrajit Mukherjee and Arindam Chowdhury

Abstract: Temporally random photo-luminescence (P-L) intermittency (or blinking) in

semiconductor nanocrystals (NCs) is generally considered to be intensity fluctuations between

‘bright’ (‘On’) and ‘dark’ (‘Off’) states, however, rarely do individual quantum-dots (QDs) exhibit

such telegraphic signal. Interestingly, while none of the blinking trajectories are identical for the same

material and morphology, even their intermittency pattern and emissivity often varies drastically from

one QD to another under identical experimental conditions. This poses a serious problem as the

exponent values (𝑚𝑂𝑛/𝑂𝑓𝑓) of the single-particle On-/Off-time durations (𝑃(𝑡𝑂𝑛/𝑂𝑓𝑓)) are used to

validate mechanistic models of NC blinking. To probe the extent of heterogeneity of blinking

processes, we sub-classify an ensemble (1040) of QDs based on the emissivity of individual QDs,

and subsequently compare the (sub)ensembles’ behaviors. The distributions of relevant blinking

parameters constructed for Mn+2 doped ZnCdS QDs reveal a remarkable variation in 𝑚𝑂𝑛/𝑂𝑓𝑓

amongst, as well as within various sub-ensembles. Our results therefore imply that multiple blinking

mechanisms being operational amongst various QDs in the ensemble. We conclude that investigation

and analyses of a large number of QDs, albeit for a limited time-span of few decades, is crucial to

characterize possible blinking mechanisms or probe heterogeneity therein.

Synthesis and Crystal Structures of Carboxylate and Phosphonate Metal–

Organic Frameworks (MOFs)

S. Senthilkumar and R. Murugavel

Abstract: The long-standing dream of researchers to be able to link molecules together into

crystalline, extended (infinite) 2D and 3D structures is now understood by the establishment of

coordination chemistry through the discovery and development of metal-organic frameworks

(MOFs). These framework materials allow compositional and structural diversity beyond

conventional solid-state materials. However, at the end of the 19th century, Alfred Werner’s work on

the geometric aspects of how ligands bind to metal ions has given rise to organometallic, bioinorganic

and cluster chemistries. By stitching together organic and inorganic units into crystalline porous

frameworks, the connectivity, spatial arrangement, and geometry of those molecular complexes can

now be fixed in space and become directly addressable. The fact that MOFs are porous provides

additional space within which molecules can further be transformed and their chemistry is controlled.

Also the process of modifying frameworks without altering their underlying connectivity, yields

isoreticular frameworks. In this regard, here we have synthesised two carboxylate and two

phosphonate centred MOFs. First one is, sterically encumbered ditopic C2-symmetric ligand based

isopropyl group decorated hydrophobic isoreticular 2D and 3D Zn-framework. And the second one

is C3-symmetric ligand tris(methylene))tris(phosphonic acid) based Al as well as Mg-frameworks.

All these frameworks are well characterised and clear structure obtained by single crystal X-ray

diffraction. These two phosphonate frameworks candidates are considered as a good proton-

conducting material because of their high crystallinity and well-designed pores for proton-conducting

pathways.

Resistive Random Access Memory Devices by Different Organic–Inorganic

Hybrid Perovskites

Itisha Dwivedi, Pramiti Hui and Chandramouli Subramaniam

Abstract: Resistive memory devices, and in particular memories based on low-cost, solution-

processable and chemically tunable organic materials, are promising alternatives explored by the

industry. Such devices exhibit high switching voltage and thereby require higher operational power.

This also leads to resistive dissipation in the form of heat, leading to overheating of the devices and

adversely affects their reliability. Addressing this demand, we report the organic– inorganic hybrid

perovskite materials in Resistive memory devices with a remarkable appearance of switching effect

which shows high reproducibility, fast switching, excellent endurance, stability and scalability.

Perovskite employed memory devices were fabricated with a simple capacitor configuration (silicon-

metal–dielectric) consisting of Si/Au/CH3NH3PbX3 (X = I3, Br3 or Cl3) (MPI, MPB, MPC) hybrid

perovskite. The device exhibited remarkable unipolar and stable resistive switching behavior with

small on–off voltage of ˂ 2 V. In comparison to their inorganic counterparts, one noticeable advantage

of organic–inorganic hybrid perovskites lies in their facile and low temperature processability. Here,

we compare three different halide hybrid perovskite I/V in different temperature, variable voltage

Raman spectra, SEM, PXRD, UV-Visible etc. These devices can be used as resistive random access

memory (RRAM), based on the resistive switching (RS) effect originated from a sudden resistance

change, bistable state, and volatile properties. For device fabrication, first Si wafer was RCA cleaned

then 100 nm Au was coated on it by thermal evaporator. The perovskite solution (1M, DMSO solvent)

was dispensed onto the Au-Si substrate and spin-coated at 3000 RPM for 30 s in air, followed by

annealing at 80 °C for 10 min.

Figure: Optical Images of the devices (A) MPB, (B) MPC, (C) MPC. (D) I/V characteristic plot of three perovskites

(inset the photo of device attached with probe). (E) Chronoamperometry plot of device in different voltage.

Rh(II)-Catalyzed Denitrogenative Transannulation of N-Sulfonyl-1,2,3- triazolyl

Cyclohexadienones for the Synthesis of Benzofurans and Cyclopropa[cd]indole-

carbaldehydes

Geetanjali S. Sontakke, Kuntal Pal and Chandra M. R. Volla*

Abstract: A rhodium-catalyzed intramolecular denitrogenative transannulation of N-sulfonyl- 1,2,3-

triazole tethered cyclohexadienones has been achieved for the synthesis of benzofurans and

cyclopropa[cd]indole-carbaldehydes in an operationally simple procedure. Remarkably, the reaction

pathway is fully dependent on the linker heteroatom (O or N) present between the cyclohexadienone

unit and triazole moiety. In the case of O-linked triazoles, a cascade sequence consisting of

intramolecular cyclopropanation and rearrangement takes place leading to the formation of

benzofurans, while in case of N-linked triazoles, cyclopropa[cd]indole-carbaldehydes were isolated

exclusively.

Reference:

1. Sontakke, G. S.; Pal, K.; Volla, C. M. R. J. Org. Chem. 2019, 84, 12198−12208

A Systems Biology Approach to Understand Effect of Serum Level on

Mammalian Cell Cycle Progression Variability

Vinodhini Govindaraj, Atharva Karulkar, Subrot Sarma, Rahul Purwar and Sandip Kar

Abstract: Intercellular variability in cell cycle commitment and progression is often observed both

for normal and cancerous cell-types. Recent studies1 at the single cell level to quantify the cell cycle

timing variability revealed insightful information’s. However, the origin and nature of such variability

still remain to be poorly understood. Herein, we aim to unravel the effect of serum concentration

dependency of the intercellular cell cycle and phase timing variability’s using Fluorescent

Ubiquitination-based Cell Cycle Indicator (FUCCI)2 in two cancer cell lines of completely different

origin. Our study demonstrates that changing the serum concentration from low to high alters the

mean cell cycle and phase durations marginally, but significantly affects the variances observed for

different phase durations. Interestingly, the cell cycle period found to be preferentially correlating

with either G1 or S/G2/M phase durations depending on the relative ratio of the variances observed

for the G1 and S/G2/M phases under low or high serum concentration, respectively, for both the cell-

types. Additional statistical analysis shows that the slow cycling cellular population under different

regime of serum concentration governs the above mentioned variability. Our proposed minimalistic

cell cycle network model rationalizes our experimental observations, and predicts how to modify the

variances, and hence the correlation pattern of the cell cycle and phase timings in a serum dependent

manner more systematically.

References:

1. Sandler O, Mizrahi SP, Weiss N, Agam O, Simon I, & Balaban NQ. 2015. Nature, 519:

468-472.

2. Sakaue-Sawano A, Kurokawa H, Morimura T, Hanyu A, Hama H, Osawa H, Kashiwagi S,

Fukami K, Miyata T, Miyoshi H, Imamura T, Ogawa M, Masai H & Miyawaki A 2008.Cell

132:487–498

PdII, and PtII Assisted Tandem P−C Bond Breaking and P−N Bond Formation

Reactions from an Amide Functionalized Bisphosphine: Synthesis, Mechanistic,

and Structural Studies

Harish S. Kunchur and Maravanji S. Balakrishna*

Abstract: The replacement of substituents on the phosphorus center has significane in metal-

mediated synthesis and homogeneous catalysis. These replacements would employ metathesis-active

ligands, that can show non-innocent behavior 1, 2 when coordinated to transition metals.3 In this regard,

we synthesized new bisphosphine ligand 1, having amide group (CONH) as additional binding

functionality. The bisphosphine 1 shows interesting coordination modes (κ2-P,P or κ3-P,N,P) upon

treatment with transition metals. Treatment of 1 with [Pd(COD)Cl2] in 1:1 molar ratio afforded κ2-

P,P complex 2 with benzene as by-product, which is formed by tandem P–C bond breaking and P–N

bond formation in the ligand framework, similar reaction in the presence of a base yielded a PNP

pincer complex 3. Further, bisphosphine 1 on treatment with [Pd(η3-C3H5)Cl]2 in 2:1 molar ratio

afforded PNP pincer complex 3 with allyl chloride as by-product. In contrast, 1:1 reaction of 1 with

[Pd(η3-C3H5)Cl]2 afforded dinuclear complex 4. Unlike reactions with palladium, the bisphosphine 1

upon treatment with [Pt(COD)Cl2] afforded simple κ2-P,P complex 7, which on treatment with

LiHMDS gave κ2-P,P complex 8, formed by tandem P–C bond breaking, P–N bond formation and

phenyl migration from PPh2 to the metal center. Complex 7 upon refluxing in toluene or ligand 1 on

treatment with [Pt(COD)Cl2] in the presence of a base afforded platinum PNP pincer complex 9.

Mechanistic studies for the formation of complexes 2 and 8 were investigated using experimental as

well as by DFT calculations.

References:

1. Van der Vlugt, J. I. & Reek, J. N. H. Angew. Chem. Int. Ed. 2009, 48, 8832–8846.

2. Lyaskovskyy, V. & de Bruin, B. ACS Catal. 2012, 2, 270–279.

3. Lian, Z., Bhawal, B. N., Yu, P. & Morandi, B. Science, 2017, 356, 1059–1063.

Exploring the Enantioselectivity of Rh-Yanphos Catalyzed -methyl Styrene

Hydroformylation : Added Insights from Theory

Yuvraj Dangat and Raghavan B. Sunoj*

Abstract: Asymmetric hydroformylation (AHF) is an efficient methodology for producing chiral

aldehydes, which are important starting materials for pharmaceuticals and fine chemicals.1 Though

the AHF of monosubstituted alkenes, like styrene, is well established, it becomes challenging for

disubstituted alkene. Furthermore, the production of chiral aldehydes on an industrial scale is yet to

be achieved. In this regard, Zhang and coworkers2 have designed new hybrid phosphorus ligand and

successfully employed in -methyl styrene hydroformylation Scheme 1. Density functional theory

calculations have been employed to explore the factors controlling the enantioselectivity of this

important process. The calculations suggest that the migratory insertion of alkene is an

enantioselective step and the noncovalent interactions (mainly C­H···) between substrate and

catalyst governs the enantio-selectivity.

Scheme: -methyl styrene.

References:

1. Franke, R.; Selent, D.; Borner, A. Chem. Rev. 2012, 112, 5675−5732.

2. You, C.; Li, S,; Li, X.;

Lan, J.;

Yang, Y.;

Chung, L. W.;

Lv, H.;

Zhang, X. J. Am. Chem.

Soc. 2018, 140, 4977−4981.

CHORh(acac)(CO)2(0.05mol%), L (0.15 mol%)

CO/H2 =2.5/2.5 bar, toluene, 80 oc, 90h, S/C=2000

TON=1720S1 PS

10 mmol, 1.18 g

1.25 g

84% yield, 87% ee

PAr2

N P

O

O

Bn

Ar = 3,5 tBu-C6H3

L=

Influence of Counter-Anion on the Zero Field Splitting of Tetrahedral Co(II)

Thiourea Complexes

Shalini Tripathi, Shefali Vaidya, Kamal Uddin Ansari, Naushad Ahmed, Eric Rivière, Lena

Spillecke, Changhyun Koo, Rüdiger Klingeler, Talal Mallah, Gopalan Rajaraman

and Maheswaran Shanmugam

Abstract: Four mononuclear Co(II) complexes with pseudo-tetrahedral geometry were isolated with

different counter anions; their structure solution reveals the molecular formula as [Co(L1)4]X2

(where L1 = thiourea (NH2-CS-NH2), X= NO3 (1), Br (2), I (3)) and [Co(L1)4](SiF6) (4)). The

detailed analysis of dc magnetic data reveals a zero-field splitting (ZFS; D) with the MS = ±3/2 as

the ground levels (D < 0) for the four complexes. The magnitude of the ZFS parameter is larger, in

absolute value, for 1 (D = -61.7 cm-1) than the other three complexes (-9.07 cm-1, -8.43 cm-1 and -

12.2 cm-1 for 2, 3 and 4 respectively). The sign of D for 1, 2 and 4 was unambiguously determined

by X-band EPR spectroscopy of the diluted samples (10 %) at 5 K. For 3, the sign of D naturally

endorsed from the frequency dependent out-of-phase signal

external dc magnetic field. It was further unequivocally confirmed by HF-EPR (70 – 600 GHz)

experiments performed on a representative pure polycrystalline 3 that gave a value of -5.1(1) cm-1.

Further, the drastic change in Spin Hamiltonian (SH) parameters and their related relaxation dynamics

phenomenon were rationalized using ab initio CASSCF/NEVPT2 calculations. Calculations disclose

that the structural distortion observed in 2-4 (due to the various anions in the crystal lattice) leads to

a non-favourable overlap between the π orbital of Co(II) and the π* orbital of the sulfur atom that

reduces the overall |D| value in these complexes compared to 1. The present study demonstrates that

not only the first but also the second coordination sphere significantly influences the magnitude of

the ZFS parameters. Particularly reduction of D up to ~90% has been witnessed (in 2-4 compared to

1) upon varying simply the counter-anions and offering a viable approach to modulate ZFS in

transition metal-containing SMMs.

Synthesis of Methyleugenol and Estargol Induced DNA Damages to Study

Translesion DNA Synthesis

Priyanka U. Deshmukh and Pradeep Kumar P. I.

Abstract: DNA damage is a well-established event responsible for carcinogenesis. DNA damaging

agents mainly cause modification at the nucleobases and disturb the W-C base pairing, which can

hamper DNA replication process by stalling replication fork. The fork can be rescued by translesion

synthesis (TLS), which is a DNA damage tolerance pathway. Methyleugenol (ME) and Estragole

(EG) are secondary metabolites found in herbs and spices (e.g. basil, pimento). It is known to form

N2 -dG DNA and N6-dA DNA adducts,1,2 which are responsible for carcinogenic activity in rat and

mouse. Herein, we report the synthesis of N2-ME-2’-dG adduct, N2 -EG-2'-dG, and N6 -ME-2'-dA

for their incorporation into DNAs.The damaged DNAs were synthesized using by solid phase

synthesis. Primer extension studies with Klenow fragment exo- (KF-)3, showed that incorporation of

correct base across modified dG with negligible extension. Further, we plan to carryout functional

and structural studies using human TLS polymerases Pol and Pol .

References:

1. McCulloch, S. D.; Kunkel, T. A. Cell Res. 2008, 18, 148-161.

2. Glatt. H. R. and Mienl. W.; K. Herrmann, W. Engst, S. Florian, A. Lampen. Toxicol. Res.

2016, 5, 808-818.

3. Pratibha P. Ghodke, S. Harikrishna, and P. I. Pradeepkumar. J. Org. Chem., 2015, 80, 2128-

2138.

Excess Electron Interactions with Solvated GC Base Pair: QM/MM Study

Ranga Santosh, Achintya KumarDutta

Abstract: We have investigated the effect of aqueous environment on the electron attachment process

to solvated Guanine-Cytosine (GC) base-pair. Since it happens in the ultrafast scale, the response of

the solvent (water) is important to understand the mechanism of electron attachment. In most of the

available implicit solvation models, solvent is treated as a structureless and with some dielectric

properties. Indeed, electron attachment through charge dipole interactions needs explicit environment

of solvent molecules which enhances the rate of electron attachment. To imitate the real life

environment and also to achieve the qualitative accuracy of experimental values of thermodynamic

properties, one has to treat the solvent explicitly which stabilizes the solute environment via hydrogen

bonding.

Our QM/MM results shows that the nuclear degrees of freedom of both water and GC base pair is

important to understand the electron transfer mechanism. The initial electron attached state is

localized on the water, and the GC bound anionic states appears as an excited state of the water-bound

ground state of the GC anion. The system undergoes a rapid reorganization of geometry following

the electron attachment, and the excess electron is localized around the cytosine in the GC base pair

within 5 fs, which is in contradiction with the previously reported DFT results. Our study shows that

the water molecules plays a cruscial role in stabilizing the anionic state by the extended hydrogen-

bonding network and enhances the rate of radiation damage in biological systems.

Figure: a) Transformation of water bound to the valence bound b) Potential Energy curve for the GC micro-solvated

base pair.

References

1) J. Phys. Chem. A2008,112,6217-6226.

2) J. Phys. Chem. B 2008,112,5189-5198.

3) Phys. Rev. Lett.2011, 106, 238108.

Stereoselective synthesis of tetrahydrocyclohepta[b]indole derivatives by

cascade radical cyclization of 3-propargylated-2-alkenyl indoles

Sanyog Kumari, Santosh J. Gharpure*

Abstract: Cyclohepta[b]indoles are privileged scaffolds owing to their presence in various bioactive

molecules and pharmacophores.1-2 Synthesis of these scaffolds has been achieved by metal mediated

reactions. Based on our ongoing effort for the synthesis of heterocycles using radical cyclization3-5

we have developed an efficient 6-exo-trig radical cyclization-cyclopropanation-ring expansion

cascade of 3-propargyl-2-alkenyl indole for the rapid synthesis of cyclohepta[b]indole in a highly

diastereoselective manner. Using the developed protocol various substituted cyclohepta[b]indole

derivatives has been synthesized in good yield with excellent diastereoselectivity.

References:

1. Cai, L.; Zhang, K.; Kwon, O. J. Am. Chem. Soc. 2016, 138, 3298.

2. Gritsch, P. J.; Stempel, E.; Gaich, T. Org. Lett. 2013, 15, 5472.

3. Gharpure, S. J.; Niranjana, P.; Porwal, Suheel K. Org. Lett. 2012, 14, 5476.

4. Gharpure, S. J.; Shelke, Y. G. Org. Lett. 2017, 19, 5022.

5. Gharpure, S. J.; Padmaja; Prasath, V,; Shelke, Y. G. Org. Lett. 2019, 21, 223.

A Dressed Coupled Cluster Theory for Molecular Energetics: Hydrogen-Bonded

& Strongly Correlated Systems

Anish Chakraborty, Rahul Maitra

Abstract: Non-covalent forces are ubiquitous in nature. The existing ab-initio theories often require

large basis set and high computational scaling to account for the same in a qualitatively correct

manner. This often restricts the applicability of these methods to small sized systems. In order to

circumvent this problem, I shall propose a dual exponential Ansatz based recursive similarity

transformed Coupled Cluster methodology, which accurately captures non-covalent interactions in

an affordable manner. The superior accuracy of the proposed method is ensured by the inclusion of

high rank correlation effects and a balanced treatment of screened Coulomb interactions. Our method

strikes the right balance between computational cost and accuracy, and thus promises to be a black-

box electronic structure tool in near future. We shall demonstrate the efficacy of the formulation with

a number of numerical examples on difficult systems with arbitrarily complex electronic

configurations. Further, I shall show a road-map within the framework of our theory to handle

strongly correlated molecular systems.

Redox Assisted Oxidative C-C Cleavage in Diruthenium

Complexes of 2,2'-Pyridil

Farheen Fatima Khan; G. K. Lahiri*

Abstract: Cleaveage of C-C bond has remained as a significant research domain due to its inevitable

implications in utilization of biomass during fuel production, in biomimicry, in waste management

for breaking down organic contaminants, etc.1 Low valent transition metal complexes have been

widely explored in this regard due to their ability to back donate electron density into the anti-bonding

orbitals of C-C bonds. On similar lines, our recent work exploited 2,2'-Pyridil and its analogue

(N1,N2-diphenyl-1,2-di(pyridin-2-yl)ethane-1,2-diimine) in diruthenium frameworks and

intriguingly varying responses were observed for the two on exposure to atmospheric oxygen.2 The

observations were further scrutinized and established by experiments and theoretical calculations

which extended interesting insights into redox mediated

oxidative cleavage of C-C bond.

References

1. C. J. Allpress, L. M. Berreau, Coord. Chem. Rev., 2013, 257, 3005-3029.

2. F. F. Khan, S. Sobottaka, B. Sarkar and G. K. Lahiri, Chem. Eur. J., 2019, 00

Solvent Mediated Relaxation Dynamics of Core-Shell Au-SiO2 Nanoparticles

Hemen Gogoi, Bala Gopal Maddala, Anindya Datta

Abstract: The inherent plasmonic property of nanosized gold particles makes it useful for various

applications ranging from photovoltaics to photothermal therapy.1 The crucial heat dissipation

dynamics of these nanostructures can be effectively probed with the help of transient absorption

spectroscopy. This technique helps us to understand the different pathways involved in the relaxation

dynamics of excited Au-SiO2 core-shell nanoparticles.2 Initially gold nanoparticles are synthesized

by reducing the gold precursor and then coated with silica by using tetraethyl orthosilicate (TEOS) to

enhance its stability.3 Synthesized nanoparticles were dispersed in solvents with different thermal

conductivities. By exciting the solutions with a strong laser pulse, the evolution of the excited state

dynamics in different surrounding environment has been monitored. The electron-phonon relaxation

time of Au-SiO2 nanoparticles has been found to be increased with decrease in thermal conductivity

of the solvent while the phonon-phonon relaxation time remains unaffected.

References:

1. Carattino, A.; Caldarola, M.; Orrit, M. Nano Lett.2018, 18, 874.

2. Mohamed, M. B.; Ahmadi, T. S.; Link, S.; Braun, M.; El-Sayed, M. A. Chem. Phys.

3. Lett.2001, 343, 55.

4. Fernández-López, C.; Mateo-Mateo, C.; Álvarez-Puebla, R. A.; Pérez-Juste, J.; Pastoriza

5. Santos, I.; Liz-Marzán, L. M. Langmuir2009, 25, 13894.

Facile Synthesis of Fused Core-Modified Sapphyrins

Prosenjit Isar and M. Ravikanth*

Abstract: Sapphyrins1are the oldest memberof expanded porphyrin family whichare 22π aromatic

pentapyrrolic systems. Sapphyrins can be used as MRI contrasting agents,multimetallic chelates for

catalysis, receptor for anions,models for aromaticity and photosensitizers in photodynamic therapy.

Core modification by replacing one or two pyrroles in sapphyrins with other five-membered

heterocycles such as thiophene, furan, selenophene, benzene2 etc alters the photophysical and

chemical properties significantly. The fused benzodipyrrole-derived sapphyrins have stronger effect

on the electronic properties to that of π-extended sapphyrin analogues because of the rigidity of the

bipyrrole unit. However, the available synthetic routes are long and requires not so easily accessible

precursors. Herein, we are presenting a facile and shortest synthetic routes for oxabenzosapphyrins

and p-benzibenzosapphyrins (Chart) using readily available precursors. The structural, spectral and

electrochemical studies of these macrocycles show interesting properties.

Chart

References:

1. Chatterjee, T.; Srinivasan, A.; Ravikanth, M.; Chandrashekar, T. K. Chem. Rev.2017, 117 (4),

3329–3376.

2. Sengupta, R.; Thorat, K. G.; Ravikanth, M. J. Org. Chem.2018, 83 (19), 11794–11803.

Wet and dry internal friction can be measured with the Jarzynski equality

R. Kailasham, Rajarshi Chakrabarti, J. Ravi Prakash

Abstract: The existence of two types of internal friction [1]—wet and dry—is revisited, and a simple

protocol is proposed for distinguishing between the two types and extracting the appropriate internal

friction coefficient. The scheme requires repeatedly stretching the polymer molecule, and measuring

the average work dissipated in the process by applying the Jarzynski equality. The internal friction

coefficient [2] is then estimated from the average dissipated work in the hypothetical limit of zero

solvent viscosity. The validity of the protocol is established through analytical calculations on a one-

dimensional Hookean spring-dashpot, and Brownian dynamics simulations of a single-mode

nonlinear spring-dashpot model for a polymer which incorporates fluctuating hydrodynamic

interactions [3]. The protocol is then used to analyze stretching simulations on a single polymer chain

with cohesive interactions between the beads, and the internal friction due to such intra-chain

interactions is shown to be of the wet type. Well-established single-molecule manipulation

techniques, such as optical tweezer-based pulling, can be used to implement the suggested protocol

experimentally.

References:

[1] A. Soranno, B. Buchli, D. Nettels, R. R. Cheng, S. Muller-Spath, S. H. Pfeil, A. Hoffmann, E. A.

Lipman, D. E. Makarov, B. Schuler, Proc. Natl. Acad. Sci. U. S. A. 109, 17800 (2012).

[2] N. Samanta and R. Chakrabarti, Phys. A 450, 165 (2016).

[3] R. Kailasham, R. Chakrabarti, and J. R. Prakash, J. Chem. Phys. 149, 094903 (2018).

Iron(III)/O2-Mediated Regioselective Oxidative Cleavage of

1-Arylbutadienes to Cinnamaldehydes

Amit Bhowmik and Rodney A. Fernandes*

Abstract: Cinnamaldehyde have various synthetic applications and its numerous derivatives are

commercially useful in food, cosmetic industries and also show various biological activities.1,2 Due to

their wide applications in organic synthesis as well as in industrial use, several methodologies have

been developed so far for their synthesis.3 However, eco-friendly and efficient methods for the

preparation of cinnamaldehydes still remains a challenge for organic chemists. Herein,

Fe2(SO4)3.nH2O/O2 has been used for oxidative regioselective cleavage of 1-arylbutadienes

tocinnamadlehydeswith excellent yields.4 The key features of this methodology are, it offers excellent

regioselectivity, environmentally friendly conditions, functional group tolerant, simple and mild

reaction conditions. The present oxidative cleavage method was employed in the synthesis of bioactive

substituted sinapaldehydes5 and the trienone curcuminoids.6 The details of this work will be presented.

References

1. Fang, J. M.; Chen, S. A.; Cheng, Y. S. J. Agric. Food Chem. 1989, 37, 744.

2. Ishida, S.; Matsuda, A.; Kawamura, Y.; Yamanaka, K. Chemotherapy 1960, 8, 157.

3. Nordqvist, A.; Björkelid, C.; Andaloussi, M.; Jansson, A. M.; Mowbray, S.; Karlen, A.;

Larhed, M. J. Org. Chem. 2011, 76, 8986.

4. Bhowmik, A.; Fernandes, R. A. Manuscriptin preparation.

5. Zhao,Y.; Hao, X.; Lu, W.; Cai, J.; Yu, H.; Sevénet, T.; Guéritte, F. J. Nat. Prod. 2002, 65,

902.

6. Chuprajob, T.; Changtam, C.; Chokchaisiri, R.; Chunglok, W.; Sornkaew, N.; Suksamrarn,

A. Bioorg. Med. Chem. Lett. 2014, 24, 2839.

Biophysical Insights into the Spatially Organized Cell Envelope of

Mycobacterium smegmatis.

Pranav Adhyapak, Shobhna Kapoor

Abstract: Mycobacterium tuberculosis, the etiological agent of tuberculosis, possesses an atypical

cell envelope comprising of peptidoglycan-arabinogalactan complex with covalently bound mycolic

acids (C60-C90) and lipids accounting for 40% of its dry weight. The cell envelope lipids are known

to form an impermeable barrier against an array of antimicrobial drugs, aiding mycobacterial survival

and resistance. The decisive role of each of the spatially organized lipid component of mycobacterial

cell envelope is not yet fully understood. We aimed to isolate and study distinct components of

mycobacterial envelope from Mycobacterium smegmatis mc2155 using steady state fluorescence

spectroscopy, atomic force microscopy, infra-red spectroscopy, and confocal microscopy to gain an

insight into phase state behavior and nanomechanical properties of these lipids. These studies will

pave way to design an effective mimic of mycobacterial membrane that can be used as a model

membrane to test membrane perturbing activity of number of bioactive compounds.

Reference:

1. Ritu Bansal-Mutalik, Mycobacterial outer membrane is a lipid bilayer and the inner

membrane is unusually rich in diacyl phosphatidylinositol dimannosides, PNAS 111 (2014)

4958-4963.

2. B. Zuber, M. Chami, C. Houssin, J. Dubochet, G. Griffiths, M. Daffe, Direct visualization of

the outer membrane of mycobacteria and corynebacteria in their native state, J. Bacteriol. 190

(2008) 5672–5680.

Synthesis of Hole Transport Materials Using Pentiptycene Core as the Building Block

Ratika Maini and Anil Kumar*

Abstract: Pentiptycene comes under the class of iptycene family. The propeller structure, thermal

and structural stability1, high glass transition temperature of the molecule has gained popularity in

widespread applications like TNT sensor2, molecular brakes, supramolecular chemistry. The

presentation talks about its candidature as transport material in Photovoltaic applications.

Pentiptycene based donor-bridge-donor derivatives (P(a), P(b), P(c), P(d) have been synthesized. The

optical and the electrochemical behavior gives HOMO and LUMO level of the compounds which

opens up the possibility of pentiptycene based compounds as an application in Hole transport layer.

References:

(1) Yang, J.-S.; Swager, T. M. Journal of the American Chemical Society1998, 120, 11864.

(2) Yang, J.-S.; Lin, C.-S.; Hwang, C.-Y. Organic Letters2001, 3, 889.

Carrageenan Beads Incorporated Fluorophoric Calix[4]arene Conjugate for

Selective, Efficient, Reversible and Fingerprint Detection of Trinitrophenol

Ashiv Narula, Aekta Upadhyay and Chebrolu Pulla Rao

Abstract: A fluorescent naphthalimide conjugate of calix[4]arene (L1) has been demonstrated for

selective and efficient detection of trinitrophenol (TNP) among nine other nitroaromatic compounds

(NACs) using the absorption and fluorescence spectroscopy. The minimum detection limit (LOD)

was found to be 29 nM, which is the lowest reported so far by any conjugate of calixarene and the

Stern-Volmer constant is also as high as (3.3±0.4) x 105 M-1. Both the SEM and TEM microscopy

reveals pores network of the probe L1 were filled with fibril structures upon addition of TNP. The

probe L1 is coated onto a whatman filter paper and utilised for fingerprint sensing of TNP. The 1H-

NMR titration and the studies carried out using the control molecule ‘C1’ (deprived of calixarene)

supports the necessity of both the naphthalimide moiety and the calixarene derivative. The probe L1

is incorporated into the carrageenan beads (L1@Cb) for the reversible sensing of TNP. The solid state

detection of TNP has also been demonstrated using the lyophilized L1@Cb bead powder using the

fluorescence microscope.

Selective & Efficient

But Not-reversible

Method-I

Method-II

Probe incorporated

Carrageenan beads

KCl TNP KCl

Reversible

Fluorescent

beads

Fluorescence

quenches

Design and Synthesis of Highly Dense Homocubane Derivatives

Sohan Lal, Neeraj Kumbhakarna, Arindrajit Chowdhury, Irishi N. N. Namboothiria*

Abstract: Polycyclic cage compounds have received tremendous attention in diverse aspects of

science such as High Energy Density Materials (HEDMs), catalysis, pharmaceuticals,natural product

synthesis and in medicinal chemistry.1-5 These diverse applications are due to their distinctive

properties, such as severely strained molecular structures, rigidity and lipophilic nature. Cage

compounds are a new class of potential HEDMs with severely strained molecular structures. This

study demonstrates the synthesis, thermodynamic characterization and energetic properties of highly

dense homocubane-based compounds, which have been synthesized, for the first time in good to

excellent yields. These compounds have higher HOF and higher energy densities than traditional

hydrocarbon fuels. Gas phase densities, gas phase HOF and their geometry were calculated with

B3LYP/6-31++G(d,p). In general the calculated HOF, densities (ρ) and density specific impulse

(ρIsp,vac) of these compounds turn out to be extremely high which is typical of high-nitrogen and

halogenated compounds. Ballistic properties such as vacuum specific impulse (Isp) and density

vacuum specific impulse (ρIsp) were calculated using the NASA CEA (Chemical Equilibrium and

Applications) utility. The compounds can be used as standalone fuels in liquid bipropellant systems,

or as additives in liquid and solid propellants.

References

1. Agrawal, J. P. Prog. Energ. Comb. Sci., 1998, 24, 1.

2. Eaton, P. E.; Cole, T. W. J. Am. Chem. Soc, 1964, 86, 3157.

3. Lal, S.; Rajkumar, S.; Tare, A.; Rashmi, S.; Chowdhury, A.; Namboothiri, I. N. N. Chem.

Asian J. 2014, 9, 3533.

4. Lal, S.; Mallick, M.; Rajkumar, S.; Oommen, O. P.; Reshmi, S.; Kumbhakarna, N.;

Chowdhury, A.; Namboothiri, I. N. N. J. Mater. Chem. A. 2015, 3, 22118.

5. Mallick, L.; Lal, S.; Reshmi, S.; Namboothiri, I. N. N.; Chowdhury, A.; Kumbhakarna, N.

New J. Chem. 2017, 41, 920.